Multi-layer-core golf ball having highly neutralized polymer outer core layer

ABSTRACT

A golf ball including an inner core layer formed from a thermoset rubber composition and having a first surface hardness; a thermoplastic outer core layer having a second surface hardness, an inner surface hardness, and being formed from a copolymer of ethylene and an α,β-unsaturated carboxylic acid, an organic acid or salt thereof, and sufficient cation source to fully-neutralize the acid groups of the copolymer; an inner cover layer; and an outer cover layer; wherein the first surface hardness is less than the second surface hardness by at least 5 Shore C and less than the inner surface hardness by at least 5 Shore C.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of co-pending U.S. patent applicationSer. No. 12/238,511, filed Sep. 26, 2008, which is acontinuation-in-part of U.S. patent application Ser. No. 12/208,631,filed Sep. 11, 2008 and now U.S. Pat. No. 8,007,375, which is acontinuation of co-pending U.S. patent application Ser. No. 11/347,456,filed Feb. 3, 2006 and now U.S. Pat. No. 7,652,08, which is acontinuation-in-part of U.S. Pat. No. 7,230,045, filed Oct. 6, 2004,which is a continuation-in-part of U.S. Pat. No. 6,939,907, filed Feb.6, 2003, which is a continuation-in-part of U.S. Pat. No. 6,756,436,filed Apr. 9, 2002, which claims priority to U.S. Provisional PatentApplication No. 60/301,046, filed Jun. 26, 2001, now abandoned, all ofwhich are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention is directed to golf ball compositions and, inparticular, polymer compositions including highly-neutralized polymersand blends thereof.

BACKGROUND OF THE INVENTION

Conventional golf balls can be divided into two general classes: solidand wound. Solid golf balls include one-piece, two-piece (i.e., solidcore and a cover), and multi-layer (i.e., solid core of one or morelayers and/or a cover of one or more layers) golf balls. Wound golfballs typically include a solid, hollow, or fluid-filled center,surrounded by a tensioned elastomeric material, and a cover. It is alsopossible to surround a hollow or fluid-filled center with a plurality ofsolid layers. Solid balls have traditionally been considered longer andmore durable than wound balls, but many solid constructions lack the“feel” provided by the wound construction.

More recently, by altering ball construction and composition,manufacturers have been able to vary a wide range of playingcharacteristics, such as compression, velocity, “feel,” and spin,optimizing each or all for various playing abilities. In particular, avariety of core and cover layer(s) constructions, such as multi-layerballs having dual cover layers and/or dual core layers, have beeninvestigated and now allow many non-wound balls to exhibitcharacteristics previously maintainable in a solid-construction golfball. These golf ball layers are typically constructed with a number ofpolymeric compositions and blends, including polybutadiene rubber,polyurethanes, polyamides, and ethylene-based ionomers.

Ionomers, and in particular ethylene α,β-ethylenically unsaturatedcarboxylic acid copolymers or a melt processible ionomer thereof, are apreferred polymer for many golf ball layers. One problem encounteredwith the use of ionomers as stiff layers, however, is theunprocessability of the material as the percent of neutralization of theacid group increases. Ionomers are stiffened by increasing the amount ofneutralization by a metal cation or a salt thereof. Once the percent ofneutralization is greater than about 60% (depending on metal cationselected), the melt flow of the ionomer becomes too low and the ease ofprocessablilty decreases or disappears altogether.

There is a need, therefore, for ionomer compositions that areneutralized at high percentages, but in a manner that still allowsresultant polymer compositions to be processible. The present inventiondescribes such compositions and there use in a variety of golf ball coreand cover layers.

SUMMARY OF THE INVENTION

The present invention is directed to a golf ball comprising a centercomprising a highly-neutralized thermoplastic copolymer of ethylene andan α,β-unsaturated carboxylic acid, the acid being 100% neutralized by asalt of an organic acid, a cation source, or a suitable base of theorganic acid; a cover; and an intermediate layer disposed between thecenter and the cover; wherein the golf ball has a first coefficient ofrestitution of 0.81 or greater when measured at an incoming velocity of125 ft/s; and a sphere resulting from a combination of the center andthe intermediate layer has a compression of 60 or greater.

The cation source is typically a metal cation of lithium, sodium,potassium, magnesium, calcium, barium, lead, tin, zinc, and aluminum.Ideally, the salt of an organic acid includes an organic acid, such asaliphatic organic acids, aromatic organic acids, saturated mono- ormulti-functional organic acids, unsaturated mono- or multi-functionalorganic acids, and multi-unsaturated mono- or multi-functional organicacids. The salt of an organic acid may include stearic acid, behenicacid, erucic acid, oleic acid, linoelic acid or dimerized derivativesthereof. The salt of an organic acid includes a cation, such as barium,lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium,strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver,aluminum, tin, and calcium.

The thermoplastic polymer comprises ionomeric copolymers andterpolymers, ionomer precursors, grafted metallocene-catalyzed polymers,high-crystalline acid polymers and their ionomers, or cationic ionomers.Preferably, the cover is injection molded, cast, reaction injectionmolded, or compression molded over the core. In one embodiment, thecover comprises an inner cover layer and an outer cover layer, at leastone which comprises a polyurethane material, a polyurea material, apolyurethane-urea hybrid material, or a polyurea-urethane hybridmaterial.

The center typically has a diameter of 1.50 inches or less and theintermediate layer has a thickness of 0.090 inches or greater,preferably between 0.090 inches and 0.180 inches. The compression can be80 or greater. Additionally, the golf ball should concurrently have asecond coefficient of restitution of 0.76 or greater when measured at anincoming velocity of 160 ft/s.

The present invention is also directed to a golf ball comprising aninnermost core, a cover, and an intermediate layer disposed between theinnermost core and the cover, wherein the intermediate layer comprises ahighly-neutralized thermoplastic copolymer of ethylene and anα,β-unsaturated carboxylic acid, the acid being 100% neutralized by asalt of an organic acid, a cation source, or a suitable base of theorganic acid, and wherein a sphere resulting from a combination of thecenter and the intermediate layer has a compression of 60 or greater.

The intermediate layer should have a flexural modulus of 50,000 psi orgreater, preferably from 60,000 psi to 150,000 psi. In one embodiment,the center has a diameter of from 0.80 inches to 1.40 inches and acompression of 30 or less, and the intermediate layer has flexuralmodulus of 50,000 psi to 70,000 psi and a thickness of 0.110 inches orgreater, and the cover comprises thermoset polymer having a hardness offrom 45 Shore D to 60 Shore D and a thickness from 0.020 inches to 0.040inches. Additionally, the golf ball should concurrently have acoefficient of restitution of 0.76 or greater when measured at anincoming velocity of 160 ft/s.

Additionally, the present invention is also directed to a golf ballcomprising an innermost core, a cover, and an intermediate layerdisposed between the innermost core and the cover, wherein the corecomprises a highly-neutralized thermoplastic copolymer of ethylene andan α,β-unsaturated carboxylic acid, the acid being 100% neutralized by asalt of an organic acid, a cation source, or a suitable base of theorganic acid, and wherein a sphere resulting from a combination of thecenter and the intermediate layer has a compression of 60 or greater.

Preferably, the compression is 80 or greater. In one embodiment, thegolf ball has a coefficient of restitution of 0.80 or greater whenmeasured at an incoming velocity of 125 ft/s. The core should have adiameter of 1.500 inches or less and/or an intermediate layer having athickness of 0.090 inches or greater. Preferably, the intermediate layerthickness is between 0.090 inches and 0.180 inches. In an alternativeembodiment, the core has a compression of 60 or less. The intermediatelayer should have a flexural modulus of 50,000 psi or greater. Also, thecover can be injection molded, cast, reaction injection molded, orcompression molded over the core.

The present invention is further directed to a golf ball including aninner core layer formed from a thermoset rubber composition and having afirst surface hardness; a thermoplastic outer core layer having a secondsurface hardness, an inner surface hardness, and being formed from acopolymer of ethylene and an α,β-unsaturated carboxylic acid, an organicacid or salt thereof, and sufficient cation source to fully-neutralizethe acid groups of the copolymer; an inner cover layer; and an outercover layer. The first surface hardness is preferably less than thesecond surface hardness by at least 5 Shore C and less than the innersurface hardness by at least 5 Shore C, more preferably at least 7 ShoreC, most preferably at least 9 Shore C.

The present invention is also directed to a golf ball including an innercore layer formed from a first rubber composition and having a firstsurface hardness; an intermediate core layer formed from a second rubbercomposition; a thermoplastic outer core layer having a second surfacehardness, an inner surface hardness, and including a copolymer ofethylene and an α,β-unsaturated carboxylic acid, an organic acid or saltthereof, and sufficient cation source to fully-neutralize the acidgroups of the copolymer; an inner cover layer; and an outer cover layer.The first surface hardness is preferably less than the second surfacehardness by at least 5 Shore C and less than the inner surface hardnessby at least 5 Shore C, more preferably at least 7 Shore C, mostpreferably at least 9 Shore C.

In one embodiment, the inner core has a diameter of 0.80 inches to 1.40inches and a compression of 30 or less, and the outer core layer hasflexural modulus of 50,000 psi to 70,000 psi and a thickness of 0.110inches or greater, and the outer cover layer comprises castablethermoset polyurethane or polyurea having a hardness of from 45 Shore Dto 60 Shore D and a thickness from 0.020 inches to 0.040 inches.

In another embodiment, a core resulting from a combination of the innercore layer, the intermediate core layer, and the thermoplastic outercore layer has a compression of 60 or greater. Preferably the core has adiameter of 1.500 inches or less and the outer core layer has athickness of 0.090 inches or greater. The inner core has a first elasticmodulus and the outer core layer has a second elastic modulus less thanthe first; the inner core has a first specific gravity and the outercore layer has a second specific gravity less than the first; the innercore has a first Bashore resilience and the outer core layer has asecond Bashore resilience less than the first; or the first surfacehardness is less than the second surface hardness by at least 7 Shore Cand less than the inner surface hardness by at least 7 Shore C.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to highly-neutralized polymers andblends thereof (“HNP”) for the use in golf equipment, preferably in ballcores, intermediate layers, and/or covers. The acid moieties of theHNP's, typically ethylene-based ionomers, are preferably neutralizedgreater than about 70%, more preferably greater than about 90%, and mostpreferably at least about 100%. The HNP's can be also be blended with asecond polymer component, which, if containing an acid group, may beneutralized in a conventional manner, by the organic fatty acids of thepresent invention, or both. The second polymer component, which may bepartially or fully neutralized, preferably comprises ionomericcopolymers and terpolymers, ionomer precursors, thermoplastics,polyamides, polycarbonates, polyesters, polyurethanes, polyureas,thermoplastic elastomers, polybutadiene rubber, balata,metallocene-catalyzed polymers (grafted and non-grafted), single-sitepolymers, high-crystalline acid polymers, cationic ionomers, and thelike. HNP polymers typically have a material hardness of between about20 and about 80 Shore D, and a flexural modulus of between about 3,000psi and about 200,000 psi.

In one embodiment of the present invention the HNP's are ionomers and/ortheir acid precursors that are preferably neutralized, either filly orpartially, with organic acid copolymers or the salts thereof. The acidcopolymers are preferably α-olefin, such as ethylene, C₃₋₈α,β-ethylenically unsaturated carboxylic acid, such as acrylic andmethacrylic acid, copolymers. They may optionally contain a softeningmonomer, such as alkyl acrylate and alkyl methacrylate, wherein thealkyl groups have from 1 to 8 carbon atoms.

The acid copolymers can be described as E/X/Y copolymers where E isethylene, X is an α,β-ethylenically unsaturated carboxylic acid, and Yis a softening comonomer. In a preferred embodiment, X is acrylic ormethacrylic acid and Y is a C₁₋₈ alkyl acrylate or methacrylate ester. Xis preferably present in an amount from about 1 to about 35 weightpercent of the polymer, more preferably from about 5 to about 30 weightpercent of the polymer, and most preferably from about 10 to about 20weight percent of the polymer. Y is preferably present in an amount fromabout 0 to about 50 weight percent of the polymer, more preferably fromabout 5 to about 25 weight percent of the polymer, and most preferablyfrom about 10 to about 20 weight percent of the polymer.

Specific acid-containing ethylene copolymers include, but are notlimited to, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylicacid/n-butyl acrylate, ethylene/methacrylic acid/iso-butyl acrylate,ethylene/acrylic acid/iso-butyl acrylate, ethylene/methacrylicacid/n-butyl methacrylate, ethylene/acrylic acid/methyl methacrylate,ethylene/acrylic acid/methyl acrylate, ethylene/methacrylic acid/methylacrylate, ethylene/methacrylic acid/methyl methacrylate, andethylene/acrylic acid/n-butyl methacrylate. Preferred acid-containingethylene copolymers include, ethylene/methacrylic acid/n-butyl acrylate,ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/methylacrylate, ethylene/acrylic acid/ethyl acrylate, ethylene/methacrylicacid/ethyl acrylate, and ethylene/acrylic acid/methyl acrylatecopolymers. The most preferred acid-containing ethylene copolymers are,ethylene/(meth) acrylic acid/n-butyl, acrylate, ethylene/(meth)acrylicacid/ethyl acrylate, and ethylene/(meth) acrylic acid/methyl acrylatecopolymers.

Ionomers are typically neutralized with a metal cation, such as Li, Na,Mg, or Zn. It has been found that by adding sufficient organic acid orsalt of organic acid, along with a suitable base, to the acid copolymeror ionomer, the ionomer can be neutralized without losing processabilityto a level much greater than for a metal cation alone. Preferably, theacid moieties are neutralized greater than about 80%, preferably from90-100%, most preferably 100% without losing processability. Thisaccomplished by melt-blending an ethylene α,β-ethylenically unsaturatedcarboxylic acid copolymer, for example, with an organic acid or a saltof organic acid, and adding a sufficient amount of a cation source toincrease the level of neutralization of all the acid moieties (includingthose in the acid copolymer and in the organic acid) to greater than90%, (preferably greater than 100%).

The organic acids of the present invention are aliphatic, mono- ormulti-functional (saturated, unsaturated, or multi-unsaturated) organicacids. Salts of these organic acids may also be employed. The salts oforganic acids of the present invention include the salts of barium,lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium,strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver,aluminum, tin, or calcium, salts of fatty acids, particularly stearic,bebenic, erucic, oleic, linoelic or dimerized derivatives thereof. It ispreferred that the organic acids and salts of the present invention berelatively non-migratory (they do not bloom to the surface of thepolymer under ambient temperatures) and non-volatile (they do notvolatilize at temperatures required for melt-blending).

The ionomers of the invention may also be partially neutralized withmetal cations. The acid moiety in the acid copolymer is neutralizedabout 1 to about 100%, preferably at least about 40 to about 100%, andmore preferably at least about 90 to about 100%, to form an ionomer by acation such as lithium, sodium, potassium, magnesium, calcium, barium,lead, tin, zinc, aluminum, or a mixture thereof.

The acid copolymers of the present invention are prepared from ‘direct’acid copolymers, copolymers polymerized by adding all monomerssimultaneously, or by grafting of at least one acid-containing monomeronto an existing polymer. Other suitable highly-neutralized acid polymercompositions are disclosed in U.S. Patent Publication Nos. 2003/0114565and 2005/0267240, and in U.S. patent application Ser. No. 11/270,066,which are incorporated herein, in their entirety, by reference.

Thermoplastic polymer components, such as copolyetheresters,copolyesteresters, copolyetheramides, elastomeric polyolefins, styrenediene block copolymers and their hydrogenated derivatives,copolyesteramides, thermoplastic polyurethanes, such ascopolyetherurethanes, copolyesterurethanes, copolyureaurethanes,epoxy-based polyurethanes, polycaprolactone-based polyurethanes,polyureas, and polycarbonate-based polyurethanes fillers, and otheringredients, if included, can be blended in either before, during, orafter the acid moieties are neutralized, thermoplastic polyurethanes.

The copolyetheresters are comprised of a multiplicity of recurring longchain units and short chain units joined head-to-tail through esterlinkages, the long chain units being represented by the formula:

and the short chain units being represented by the formula:

where G is a divalent radical remaining after the removal of terminalhydroxyl groups from a poly(alkylene oxide) glycol having a molecularweight of about 400-8000 and a carbon to oxygen ratio of about 2.0-4.3;R is a divalent radical remaining after removal of hydroxyl groups froma diol having a molecular weight less than about 250; provided saidshort chain ester units amount to about 15-95 percent by weight of saidcopolyetherester. The preferred copolyetherester polymers are thosewhere the polyether segment is obtained by polymerization oftetrahydrofuran and the polyester segment is obtained by polymerizationof tetramethylene glycol and phthalic acid. For purposes of theinvention, the molar ether:ester ratio can vary from 90:10 to 10:80;preferably 80:20 to 60:40; and the Shore D hardness is less than 70;preferably less than about 40.

The copolyetheramides are comprised of a linear and regular chain ofrigid polyamide segments and flexible polyether segments, as representedby the general formula:

wherein PA is a linear saturated aliphatic polyamide sequence framedfrom a lactam or amino acid having a hydrocarbon chain containing 4 to14 carbon atoms or from an aliphatic C₆-C₈ diamine, in the presence of achain-limiting aliphatic carboxylic diacid having 4-20 carbon atoms;said polyamide having an average molecular weight between 300 and15,000; and PB is a polyoxyalkylene sequence formed from linear orbranched aliphatic polyoxyalkylene glycols, mixtures thereof orcopolyethers derived therefrom, said polyoxyalkylene glycols having amolecular weight of less than or equal to 6000; and n indicates asufficient number of repeating units so that said polyetheramidecopolymer has an intrinsic viscosity of from about 0.6 to about 2.05.The preparation of these polyetheramides comprises the step of reactinga dicarboxylic polyamide, the COOH groups of which are located at thechain ends, with a polyoxyalkylene glycol hydroxylated at the chainends, in the presence of a catalyst such as a tetra-alkyl ortho titanatehaving the general formula Ti(OR)_(x) wherein R is a linear branchedaliphatic hydrocarbon radical having 1 to 24 carbon atoms. Again, themore polyether units incorporated into the copolyetheramide, the softerthe polymer. The ether:amide ratios are as described above for theether:ester ratios, as is the Shore D hardness.

The elastomeric polyolefins are polymers composed of ethylene and higherprimary olefins such as propylene, hexene, octene, and optionally1,4-hexadiene and or ethylidene norbornene or norbornadiene. Theelastomeric polyolefins can be optionally functionalized with maleicanhydride, epoxy, hydroxy, amine, carboxylic acid, sulfonic acid, orthiol groups.

Thermoplastic polyurethanes are linear or slightly chain branchedpolymers consisting of hard blocks and soft elastomeric blocks. They areproduced by reacting soft hydroxy terminated elastomeric polyethers orpolyesters with diisocyanates, such as methylene diisocyanate (“MDI”),p-phenylene diisocyanate (“PPDI”), or toluene diisocyanate (“TDI”).These polymers can be chain extended with glycols, secondary diamines,diacids, or amino alcohols. The reaction products of the isocyanates andthe alcohols are called urethanes and these blocks are relatively hardand high melting. These hard high melting blocks are responsible for thethermoplastic nature of the polyurethanes.

Block styrene diene copolymers and their hydrogenated derivatives arecomposed of polystyrene units and polydiene units. They may also befunctionalized with moieties such as OH, NH₂, epoxy, COOH, and anhydridegroups. The polydiene units are derived from polybutadiene, polyisopreneunits or copolymers of these two. In the case of the copolymer it ispossible to hydrogenate the polyolefin to give a saturated rubberybackbone segments. These materials are usually referred to as SBS, SIS,or SEBS thermoplastic elastomers and they can also be functionalizedwith maleic anhydride.

Grafted metallocene-catalyzed polymers are also useful for blending withthe HNP's of the present invention. The grafted metallocene-catalyzedpolymers, while conventionally neutralized with metal cations, may alsobe neutralized, either partially for fully, with organic acids or saltsthereof and an appropriate base. Grafted metallocene-catalyzed polymersuseful, such as those disclosed in U.S. Pat. Nos. 5,703,166; 5,824,746;5,981,658; and 6,025,442, which are incorporated herein by reference, inthe golf balls of the invention are available in experimental quantitiesfrom DuPont under the tradenames SURLYN® NMO 525D, SURLYN® NMO 524D, andSURLYN® NMO 499D, all formerly known as the FUSABOND® family ofpolymers, or may be obtained by subjecting a non-graftedmetallocene-catalyzed polymer to a post-polymerization reaction toprovide a grafted metallocene-catalyzed polymer with the desired pendantgroup or groups. Examples of metallocene-catalyzed polymers to whichfunctional groups may be grafted for use in the invention include, butare not limited to, homopolymers of ethylene and copolymers of ethyleneand a second olefin, preferably, propylene, butene, pentene, hexene,heptene, octene, and norbornene. Generally, the invention includes golfballs having at least one layer comprising at least one graftedmetallocene-catalyzed polymer or polymer blend, where the graftedmetallocene-catalyzed polymer is produced by grafting a functional grouponto a metallocene-catalyzed polymer having the formula:

wherein R₁ is hydrogen, branched or straight chain alkyl such as methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, carbocyclic, oraromatic; R₂ is hydrogen, lower alkyl including C₁-C₅; carbocyclic, oraromatic; R₃ is hydrogen, lower alkyl including C₁-C₅, carbocyclic, oraromatic; R₄ is selected from the group consisting of H, C_(n)H_(2n+1),where n=1 to 18, and phenyl, in which from 0 to 5 H within R₄ can bereplaced by substituents COOH, SO₃H, NH₂, F, Cl, Br, I, OH, SH,silicone, lower alkyl esters and lower alkyl ethers, with the provisothat R₃ and R₄ can be combined to form a bicyclic ring; R₅ is hydrogen,lower alkyl including C₁-C₅, carbocyclic, or aromatic; R₆ is hydrogen,lower alkyl including C₁-C₅, carbocyclic, or aromatic; and wherein x, yand z are the relative percentages of each co-monomer. X can range fromabout 1 to 99 percent or more preferably from about 10 to about 70percent and most preferred, from about 10 to 50 percent. Y can be from99 to 1 percent, preferably, from 90 to 30 percent, or most preferably,90 to 50 percent. Z can range from about 0 to about 49 percent. One ofordinary skill in the art would understand that if an acid moiety ispresent as a ligand in the above polymer that it may be neutralized upto 100% with an organic fatty acid as described above.

Metallocene-catalyzed copolymers or terpolymers can be random or blockand may be isotactic, syndiotactic, or atactic. The pendant groupscreating the isotactic, syndiotactic, or atactic polymers are chosen todetermine the interactions between the different polymer chains makingup the resin to control the final properties of the resins used in golfball covers, centers, or intermediate layers. As will be clear to thoseskilled in the art, grafted metallocene-catalyzed polymers useful in theinvention that are formed from metallocene-catalyzed random or blockcopolymers or terpolymers will also be random or block copolymers orterpolymers, and will have the same tacticity of themetallocene-catalyzed polymer backbone.

As used herein, the term “phrase branched or straight chain alkyl” meansany substituted or unsubstituted acyclic carbon-containing compounds.Examples of alkyl groups include lower alkyl, for example, methyl,ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or t-butyl; upper alkyl,for example, octyl, nonyl, decyl, and the like; and lower alkylene, forexample, ethylene, propylene, butylene, pentene, hexene, octene,norbornene, nonene, decene, and the like.

In addition, such alkyl groups may also contain various substituents inwhich one or more hydrogen atoms has been replaced by a functionalgroup. Functional groups include, but are not limited to hydroxyl,amino, carboxyl, sulfonic amide, ester, ether, phosphates, thiol, nitro,silane and halogen (fluorine, chlorine, bromine and iodine), to mentionbut a few.

As used herein, the term “substituted and unsubstituted carbocyclic”means cyclic carbon-containing compounds, including, but not limited tocyclopentyl, cyclohexyl, cycloheptyl, and the like. Such cyclic groupsmay also contain various substituents in which one or more hydrogenatoms has been replaced by a functional group. Such functional groupsinclude those described above, and lower alkyl groups having from 1-28carbon atoms. The cyclic groups of the invention may further comprise aheteroatom.

As mentioned above, R₁ and R₂ can also represent any combination ofalkyl, carbocyclic or aryl groups, for example, 1-cyclohexylpropyl,benzyl cyclohexylmethyl, 2-cyclohexylpropyl, 2,2-methylcyclohexylpropyl,2,2-methylphenylpropyl, and 2,2-methylphenylbutyl.

Non-grafted metallocene-catalyzed polymers useful in the presentinvention are commercially available under the trade name AFFINITY®polyolefin plastomers and ENGAGE® polyolefin elastomers commerciallyavailable from Dow Chemical Company and DuPont-Dow. Other commerciallyavailable metallocene-catalyzed polymers can be used, such as EXACT®,commercially available from Exxon and INSIGHT®, commercially availablefrom Dow. The EXACT® and INSIGHT® line of polymers also have novelrheological behavior in addition to their other properties as a resultof using a metallocene catalyst technology. Metallocene-catalyzedpolymers are also readily available from Sentinel Products Corporationof Hyannis, Mass., as foamed sheets for compression molding.

Monomers useful in the present invention include, but are not limitedto, olefinic monomers having, as a functional group, sulfonic acid,sulfonic acid derivatives, such as chlorosulfonic acid, vinyl ethers,vinyl esters, primary, secondary, and tertiary amines, mono-carboxylicacids, dicarboxylic acids, partially or fully ester-derivatizedmono-carboxylic and dicarboxylic acids, anhydrides of dicarboxylicacids, and cyclic imides of dicarboxylic acids.

In addition, metallocene-catalyzed polymers may also be functionalizedby sulfonation, carboxylation, or the addition of an amine or hydroxygroup. Metallocene-catalyzed polymers functionalized by sulfonation,carboxylation, or the addition of a hydroxy group may be converted toanionic ionomers by treatment with a base. Similarly,metallocene-catalyzed polymers functionalized by the addition of anamine may be converted to cationic ionomers by treatment with an alkylhalide, acid, or acid derivative.

The most preferred monomer is maleic anhydride, which, once attached tothe metallocene-catalyzed polymer by the post-polymerization reaction,may be further subjected to a reaction to form a graftedmetallocene-catalyzed polymer containing other pendant or functionalgroups. For example, reaction with water will convert the anhydride to adicarboxylic acid; reaction with ammonia, alkyl, or aromatic amine formsan amide; reaction with an alcohol results in the formation of an ester;and reaction with base results in the formation of an anionic ionomer.

The HNP's of the present invention may also be blended with single-siteand metallocene catalysts and polymers formed therefrom. As used herein,the term “single-site catalyst,” such as those disclosed in U.S. Pat.No. 6,150,462 which is incorporated herein by reference, refers to acatalyst that contains an ancillary ligand that influences the stearicand electronic characteristics of the polymerizing site in a manner thatprevents formation of secondary polymerizing species. The term“metallocene catalyst” refers to a single-site catalyst wherein theancillary ligands are comprising substituted or unsubstitutedcyclopentadienyl groups, and the term “non-metallocene catalyst” refersto a single-site catalyst other than a metallocene catalyst.

Non-metallocene single-site catalysts include, but are not limited to,the Brookhart catalyst, which has the following structure:

wherein M is nickel or palladium; R and R′ are independently hydrogen,hydrocarbyl, or substituted hydrocarbyl; Ar is (CF₃)₂C₆H₃, and X isalkyl, methyl, hydride, or halide; the McConville catalyst, which hasthe structure:

wherein M is titanium or zirconium. Iron (II) and cobalt (II) complexeswith 2,6-bis(imino) pyridyl ligands, which have the structure:

where M is the metal, and R is hydrogen, alkyl, or hydrocarbyl. Titaniumor zirconium complexes with pyrroles as ligands also serve assingle-site catalysts. These complexes have the structure:

where M is the metal atom; m and n are independently 1 to 4, andindicate the number of substituent groups attached to the aromaticrings; R_(m) and R_(n) are independently hydrogen or alkyl; and X ishalide or alkyl. Other examples include diimide complexes of nickel andpalladium, which have the structure:

where Ar is aromatic, M is the metal, and X is halide or alkyl.Boratabenzene complexes of the Group IV or V metals also function assingle-site catalysts. These complexes have the structure:

where B is boron and M is the metal atom.

As used herein, the term “single-site catalyzed polymer” refers to anypolymer, copolymer, or terpolymer, and, in particular, any polyolefinpolymerized using a single-site catalyst. The term “non-metallocenesingle-site catalyzed polymer” refers to any polymer, copolymer, orterpolymer, and, in particular, any polyolefin polymerized using asingle-site catalyst other than a metallocene-catalyst. The catalystsdiscussed above are examples of non-metallocene single-site catalysts.The term “metallocene catalyzed polymer” refers to any polymer,copolymer, or terpolymer, and, in particular, any polyolefin,polymerized using a metallocene catalyst.

As used herein, the term “single-site catalyzed polymer blend” refers toany blend of a single-site catalyzed polymer and any other type ofpolymer, preferably an ionomer, as well as any blend of a single-sitecatalyzed polymer with another single-site catalyzed polymer, including,but not limited to, a metallocene-catalyzed polymer.

The terms “grafted single-site catalyzed polymer” and “graftedsingle-site catalyzed polymer blend” refer to any single-site catalyzedpolymer or single-site catalyzed polymer blend in which the single-sitecatalyzed polymer has been subjected to a post-polymerization reactionto graft at least one functional group onto the single-site catalyzedpolymer. A “post-polymerization reaction” is any reaction that occursafter the formation of the polymer by a polymerization reaction.

The single-site catalyzed polymer, which may be grafted, may also beblended with polymers, such as non-grafted single-site catalyzedpolymers, grafted single-site catalyzed polymers, ionomers, andthermoplastic elastomers. Preferably, the single-site catalyzed polymeris blended with at least one ionomer of the preset invention.

Grafted single-site catalyzed polymers useful in the golf balls of theinvention may be obtained by subjecting a non-grafted single-sitecatalyzed polymer to a post-polymerization reaction to provide a graftedsingle-site catalyzed polymer with the desired pendant group or groups.Examples of single-site catalyzed polymers to which functional groupsmay be grafted for use in the invention include, but are not limited to,homopolymers of ethylene and propylene and copolymers of ethylene and asecond olefin, preferably, propylene, butene, pentene, hexene, heptene,octene, and norbornene. Monomers useful in the present inventioninclude, but are not limited to olefinic monomers having as a functionalgroup sulfonic acid, sulfonic acid derivatives, such as chlorosulfonicacid, vinyl ethers, vinyl esters, primary, secondary, and tertiaryamines, epoxies, isocyanates, mono-carboxylic acids, dicarboxylic acids,partially or fully ester derivatized mono-carboxylic and dicarboxylicacids, anhydrides of dicarboxylic acids, and cyclic imides ofdicarboxylic acids. Generally, this embodiment of the invention includesgolf balls having at least one layer comprising at least one graftedsingle-site catalyzed polymer or polymer blend, where the graftedsingle-site catalyzed polymer is produced by grafting a functional grouponto a single-site catalyzed polymer having the formula:

where R₁ is hydrogen, branched or straight chain alkyl such as methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, carbocyclic,aromatic or heterocyclic; R₂, R₃, R₅, and R₆ are hydrogen, lower alkylincluding C₁-C₅, carbocyclic, aromatic or heterocyclic; R₄ is H,C_(n)H_(2n+1), where n=1 to 18, and phenyl, in which from 0 to 5 Hwithin R₄ can be replaced by substituents such as COOH, SO₃H, NH₂, F,Cl, Br, I, OH, SH, epoxy, isocyanate, silicone, lower alkyl esters andlower alkyl ethers; also, R₃ and R₄ can be combined to form a bicyclicring; and x, y and z are the relative percentages of each co-monomer. Xcan range from about 1 to about 100 percent or more preferably from 1 to70 percent and most preferred, from about 1 to about 50 percent. Y canbe from about 99 to about 0 percent, preferably, from about 9 to about30 percent, or most preferably, about 9 to about 50 percent. Z can rangefrom about 0 to about 50 percent. One of ordinary skill in the art wouldalso understand that if an acid group is selected as a ligand in theabove structure that it too could be neutralized with the organic fattyacids described above.

The HNP's of the present invention may also be blended with highcrystalline acid copolymers and their ionomer derivatives (which may beneutralized with conventional metal cations or the organic fatty acidsand salts thereof) or a blend of a high crystalline acid copolymer andits ionomer derivatives and at least one additional material, preferablyan acid copolymer and its ionomer derivatives. As used herein, the term“high crystalline acid copolymer” is defined as a “product-by-process”in which an acid copolymer or its ionomer derivatives formed from aethylene/carboxylic acid copolymer comprising about 5 to about 35percent by weight acrylic or methacrylic acid, wherein the copolymer ispolymerized at a temperature of about 130° C. to 200° C., at pressuresgreater than about 20,000 psi preferably greater than about 25,000 psi,more pref. from about 25,000 psi to about 50,000 psi, wherein up toabout 70 percent, preferably 100 percent, of the acid groups areneutralized with a metal ion, organic fatty acids and salts thereof, ora mixture thereof. The copolymer can have a melt index (“MI”) of fromabout 20 to about 300 g/10 min, preferably about 20 to about 200 g/10min, and upon neutralization of the copolymer, the resulting acidcopolymer and its ionomer derivatives should have an MI of from about0.1 to about 30.0 g/10 min.

Suitable high crystalline acid copolymer and its ionomer derivativescompositions and methods for making them are disclosed in U.S. Pat. No.5,580,927, the disclosure of which is hereby incorporated by referencein its entirety.

The high crystalline acid copolymer or its ionomer derivatives employedin the present invention are preferably formed from a copolymercontaining about 5 to about 35 percent, more preferably from about 9 toabout 18, most preferably about 10 to about 13 percent, by weight ofacrylic acid, wherein up to about 75 percent, most preferably about 60percent, of the acid groups are neutralized with an organic fatty acid,salt thereof, or a metal ion, such as sodium, lithium, magnesium, orzinc ion.

Generally speaking, high crystalline acid copolymer and its ionomerderivatives are formed by polymerization of their base copolymers atlower temperatures, but at equivalent pressures to those used forforming a conventional acid copolymer and its ionomer derivatives.Conventional acid copolymers are typically polymerized at apolymerization temperature of from at least about 200° C. to about 270°C., preferably about 220° C., and at pressures of from about 23,000 toabout 30,000 psi. In comparison, the high crystalline acid copolymer andits ionomer derivatives employed in the present invention are producedfrom acid copolymers that are polymerized at a polymerizationtemperature of less than 200° C., and preferably from about 130° C. toabout 200° C., and at pressures from about 20,000 to about 50,000 psi.

The HNP's of the present invention may also be blended with cationicionomers, such as those disclosed in U.S. Pat. No. 6,193,619 which isincorporated herein by reference. In particular, cationic ionomers havea structure according to the formula:

or the formula:

wherein R₁-R₉ are organic moieties of linear or branched chain alkyl,carbocyclic, or aryl; and Z is the negatively charged conjugate ionproduced following alkylation and/or quaternization. The cationicpolymers may also be quarternized up to 100% by the organic fatty acidsdescribed above.

In addition, such alkyl group may also contain various substituents inwhich one or more hydrogen atoms has been replaced by a functionalgroup. Functional groups include but are not limited to hydroxyl, amino,carboxyl, amide, ester, ether, sulfonic, siloxane, siloxyl, silanes,sulfonyl, and halogen.

As used herein, substituted and unsubstituted carbocyclic groups of upto about 20 carbon atoms means cyclic carbon-containing compounds,including but not limited to cyclopentyl, cyclohexyl, cycloheptyl, andthe like. Such cyclic groups may also contain various substituents inwhich one or more hydrogen atoms has been replaced by a functionalgroup. Such functional groups include those described above, and loweralkyl groups as described above. The cyclic groups of the invention mayfurther comprise a heteroatom.

The HNP's of the present invention may also be blended with polyurethaneand polyurea ionomers which include anionic moieties or groups, such asthose disclosed in U.S. Pat. No. 6,207,784 which is incorporated hereinby reference. Typically, such groups are incorporated onto thediisocyanate or diisocyanate component of the polyurethane or polyureaionomers. The anionic group can also be attached to the polyol or aminecomponent of the polyurethane or polyurea, respectively. Preferably, theanionic group is based on a sulfonic, carboxylic or phosphoric acidgroup. Also, more than one type of anionic group can be incorporatedinto the polyurethane or polyurea. Examples of anionic polyurethaneionomers with anionic groups attached to the diisocyanate moiety canhave a chemical structure according to the following formula:

where A=R—Z⁻M^(+x); R is a straight chain or branched aliphatic group, asubstituted straight chain or branched aliphatic group, or an aromaticor substituted aromatic group; Z=SO₃ ⁻, CO₂ ⁻ or HPO₃ ⁻; M is a groupIA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIB, VIIB orVIIIB metal; x=1 to 5; B is a straight chain or branched aliphaticgroup, a substituted straight chain or branched aliphatic group, or anaromatic or substituted aromatic group; and n=1 to 100.

Preferably, M^(+x) is one of the following: Li⁺, Na⁺, K⁺, Mg⁺², Zn⁺²,Ca⁺², Mn⁺², Al⁺³, Ti^(+x), Zr^(+x), W^(+x) or Hf^(+x).

Exemplary anionic polyurethane ionomers with anionic groups attached tothe polyol component of the polyurethane are characterized by the abovechemical structure where A is a straight chain or branched aliphaticgroup, a substituted straight chain or branched aliphatic group, or anaromatic or substituted aromatic group; B=R—Z⁻M^(+x); R is a straightchain or branched aliphatic group, a substituted straight chain orbranched aliphatic group, or an aromatic or substituted aromatic group;Z=SO₃ ⁻, CO₂ ⁻ or HPO₃ ⁻; M is a group IA, IB, IIA, IIB, IIIA, IIIB,IVA, IVB, VA, VB, VIIA, VIIB, VIIB or VIIIB metal; x=1 to 5; and n=1 to100. Preferably, M^(+x) is one of the following: Li⁺, Na⁺, K⁺, Mg⁺²,Zn⁺², Ca⁺², Mn⁺², Al⁺³, Ti^(+x), Zr^(+x), W^(+x) or Hf^(+x).

Examples of suitable anionic polyurea ionomers with anionic groupsattached to the diisocyanate component have a chemical structureaccording to the following chemical structure:

where A=R—Z⁻M^(+x); R is a straight chain or branched aliphatic group, asubstituted straight chain or branched aliphatic group, or an aromaticor substituted aromatic group; Z=SO₃ ⁻, CO₂ ⁻ or HPO₃ ⁻; M is a groupIA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIB or VIIIBmetal; x=1 to 5; and B is a straight chain or branched aliphatic group,a substituted straight chain or branched aliphatic group, or an aromaticor substituted aromatic group. Preferably, M^(+x) is one of thefollowing: Li⁺, Na⁺, K⁺, Mg⁺², Zn⁺², Ca⁺², Mn⁺², Al⁺³, Ti^(+x), Zr^(+x),W^(+x), or Hf^(+x).

Suitable anionic polyurea ionomers with anionic groups attached to theamine component of the polyurea are characterized by the above chemicalstructure where A is a straight chain or branched aliphatic group, asubstituted straight chain or branched aliphatic group, or an aromaticor substituted aromatic group; B=R—Z-M^(+x); R is a straight chain orbranched aliphatic group, a substituted straight chain or branchedaliphatic group, or an aromatic or substituted aromatic group; Z=SO₃ ⁻,CO₂ ⁻, or HPO₃ ⁻; M is a group IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB,VA, VB, VIA, VIB, VIIB or VIIIB metal; and x=1 to 5. Preferably, M^(+x)is one of the following: Li⁺, Na⁺, K⁺, Mg⁺², Zn⁺², Ca⁺², Mn⁺², Al⁺³,Ti^(+x), Zr^(+x), W^(+x), or Hf^(+x). The anionic polyurethane andpolyurea ionomers may also be neutralized up to 100% by the organicfatty acids described above.

The anionic polymers useful in the present invention, such as thosedisclosed in U.S. Pat. No. 6,221,960 which is incorporated herein byreference, include any homopolymer, copolymer or terpolymer havingneutralizable hydroxyl and/or dealkylable ether groups, and in which atleast a portion of the neutralizable or dealkylable groups areneutralized or dealkylated with a metal ion.

As used herein “neutralizable” or “dealkylable” groups refer to ahydroxyl or ether group pendent from the polymer chain and capable ofbeing neutralized or dealkylated by a metal ion, preferably a metal ionbase. These neutralized polymers have improved properties critical togolf ball performance, such as resiliency, impact strength and toughnessand abrasion resistance. Suitable metal bases are ionic compoundscomprising a metal cation and a basic anion. Examples of such basesinclude hydroxides, carbonates, acetates, oxides, sulfides, and thelike.

The particular base to be used depends upon the nature of the hydroxylor ether compound to be neutralized or dealkylated, and is readilydetermined by one skilled in the art. Preferred anionic bases includehydroxides, carbonates, oxides and acetates.

The metal ion can be any metal ion which foams an ionic compound withthe anionic base. The metal is not particularly limited, and includesalkali metals, preferably lithium, sodium or potassium; alkaline earthmetals, preferably magnesium or calcium; transition metals, preferablytitanium, zirconium, or zinc; and Group III and IV metals. The metal ioncan have a +1 to +5 charge. Most preferably, the metal is lithium,sodium, potassium, zinc, magnesium, titanium, tungsten, or calcium, andthe base is hydroxide, carbonate or acetate.

The anionic polymers useful in the present invention include those whichcontain neutralizable hydroxyl and/or dealkylable ether groups.Exemplary polymers include ethylene vinyl alcohol copolymers, polyvinylalcohol, polyvinyl acetate, poly(p-hydroxymethylene styrene), andp-methoxy styrene, to name but a few. It will be apparent to one skilledin the art that many such polymers exist and thus can be used in thecompositions of the invention. In general, the anionic polymer can bedescribed by the chemical structure:

where R₁ is OH, OC(O)R_(a), O-M^(+V), (CH₂)_(n)R_(b),(CHR_(z))_(n)R_(b), or aryl, wherein n is at least 1, R_(a) is a loweralkyl, M is a metal ion, V is an integer from 1 to 5, R_(b) is OH,OC(O)R_(a), O-M^(+V), and R_(z) is a lower alkyl or aryl, and R₂, R₃ andR₄ are each independently hydrogen, straight-chain or branched-chainlower alkyl. R₂, R₃ and R₄ may also be similarly substituted. Preferablyn is from 1 to 12, more preferably 1 to 4.

The term “substituted,” as used herein, means one or more hydrogen atomshas been replaced by a functional group. Functional groups include, butare not limited to, hydroxyl, amino, carboxyl, sulfonic, amide, ether,ether, phosphates, thiol, nitro, silane, and halogen, as well as manyothers which are quite familiar to those of ordinary skill in this art.

The terms “alkyl” or “lower alkyl,” as used herein, includes a group offrom about 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms.

In the anionic polymers useful in the present invention, at least aportion of the neutralizable or dealkylable groups of R₁ are neutralizedor dealkylated by an organic fatty acid, a salt thereof, a metal base,or a mixture thereof to form the corresponding anionic moiety. Theportion of the neutralizable or dealkylable groups which are neutralizedor dealkylated can be between about 1 to about 100 weight percent,preferably between about 50 to about 100 weight percent, more preferablybefore about 90 to about 100.

Neutralization or dealkylation may be performed by melting the polymerfirst, then adding a metal ion in an extruder. The degree ofneutralization or dealkylation is controlled by varying the amount ofmetal ion added. Any method of neutralization or dealkylation availableto those of ordinary skill in the art may also be suitably employed.

In one embodiment, the anionic polymer is repeating units any one of thethree homopolymer units in the chemical structure above. In a preferredembodiment, R₂, R₃ and R₄ are hydrogen, and R₁ is hydroxyl, i.e., theanionic polymer is a polyvinyl alcohol homopolymer in which a portion ofthe hydroxyl groups have been neutralized with a metal base. In anotherpreferred embodiment, R₂, R₃ and R₄ are hydrogen, R₁ is OC(O)R_(a), andR_(a) is methyl, i.e., the anionic polymer is a polyvinyl acetatehomopolymer in which a portion of the methyl ether groups have beendealkylated with a metal ion.

The anionic polymer can also be a copolymer of two different repeatingunits having different substituents, or a terpolymer of three differentrepeating units described in the above formula. In this embodiment, thepolymer can be a random copolymer, an alternating copolymer, or a blockcopolymer, where the teen “copolymer” includes terpolymers.

In another embodiment, the anionic polymer is a copolymer, wherein R₅,R₆, R₇ and R₈ are each independently selected from the group definedabove for R₂. The first unit of the copolymer can comprise from about 1to 99 percent weight percent of the polymer, preferably from about 5 to50 weight percent, and the second unit of the copolymer can comprisefrom about 99 to 1 weight percent, preferably from about 95 to 50 weightpercent. In one preferred embodiment, the anionic polymer is a random,alternating or block copolymer of units (Ia) and (Ib) wherein R₁ ishydroxyl, and each of the remaining R groups is hydrogen, i.e., thepolymer is a copolymer of ethylene and vinyl alcohol. In anotherpreferred embodiment, the anionic polymer is a random, alternating orblock copolymer of units (Ia) and (Ib) wherein R₁ is OC(O)R₅, where R₅is methyl, and each of the remaining R groups is hydrogen, i.e., thepolymer is a copolymer of ethylene and vinyl acetate.

In another embodiment, the anionic polymer is an anionic polymer havingneutralizable hydroxyl and/or dealkylable ether groups of as in theabove chemical structure wherein R₁₋₉ and R_(b) and R_(z) are as definedabove; R₁₀₋₁₁ are each independently selected from the group as definedabove for R₂; and R₁₂ is OH or OC(O)R₁₃, where R₁₃ is a lower alkyl;wherein x, y and z indicate relative weight percent of the differentunits. X can be from about 99 to about 50 weight percent of the polymer,y can be from about 1 to about 50 weight percent of the polymer, and zranges from about 0 to about 50 weight percent of the polymer. At leasta portion of the neutralizable groups R₁ are neutralized. When theamount of z is greater than zero, a portion of the groups R₁₀ can alsobe fully or partially neutralized, as desired.

In particular, the anionic polymers and blends thereof can comprisecompatible blends of anionic polymers and ionomers, such as the ionomersdescribed above, and ethylene acrylic methacrylic acid ionomers, andtheir terpolymers, sold commercially under the trade names SURLYN® andIOTEK® by DuPont and Exxon respectively. The anionic polymer blendsuseful in the golf balls of the invention can also include otherpolymers, such as polyvinylalcohol, copolymers of ethylene and vinylalcohol, poly(ethylethylene), poly(heptylethylene),poly(hexyldecylethylene), poly(isopentylethylene), poly(butyl acrylate),acrylate), poly(2-ethylbutyl acrylate), poly(heptyl acrylate),poly(2-methylbutyl acrylate), poly(3-methylbutyl acrylate),poly(N-octadecylacrylamide), poly(octadecyl methacrylate),poly(butoxyethylene), poly(methoxyethylene), poly(pentyloxyethylene),poly(1,1-dichloroethylene), poly(4-[(2-butoxyethoxy)methyl]styrene),poly[oxy(ethoxymethyl)ethylene], poly(oxyethylethylene),poly(oxytetramethylene), poly(oxytrimethylene), poly(silanes) andpoly(silazanes), polyamides, polycarbonates, polyesters, styrene blockcopolymers, polyetheramides, polyurethanes, main-chain heterocyclicpolymers and poly(furan tetracarboxylic acid diimides), as well as theclasses of polymers to which they belong.

The anionic polymer compositions of the present invention typically havea flexural modulus of from about 500 psi to about 300,000 psi,preferably from about 2000 to about 200,000 psi. The anionic polymercompositions typically have a material hardness of at least about 15Shore A, preferably between about 30 Shore A and 80 Shore D, morepreferably between about 50 Shore A and 60 Shore D. The loss tangent, ordissipation factor, is a ratio of the loss modulus over the dynamicshear storage modulus, and is typically less than about 1, preferablyless than about 0.01, and more preferably less than about 0.001 for theanionic polymer compositions measured at about 23° C. The specificgravity is typically greater than about 0.7, preferably greater thanabout 1, for the anionic polymer compositions. The dynamic shear storagemodulus, or storage modulus, of the anionic polymer compositions atabout 23° C. is typically at least about 10,000 dyn/cm².

The golf balls of the present invention may comprise a variety ofconstructions. In one embodiment of the present invention, golf ballincludes a core, an inner cover layer surrounding the core, and an outercover layer. Preferably, the core is solid. More preferably, the core isa solid, single-layer core. In a preferred embodiment, the solid corecomprises the HNP's of the present invention. In an alternativeembodiment, the solid core may include compositions having a baserubber, a crosslinking agent, a filler, and a co-crosslinking orinitiator agent, and the inner cover layer comprises the HNP's of thepresent invention.

The base rubber typically includes natural or synthetic rubbers. Apreferred base rubber is 1,4-polybutadiene having a cis-structure of atleast 40%. More preferably, the base rubber compriseshigh-Mooney-viscosity rubber. If desired, the polybutadiene can also bemixed with other elastomers known in the art such as natural rubber,polyisoprene rubber and/or styrene-butadiene rubber in order to modifythe properties of the core.

The crosslinking agent includes a metal salt of an unsaturated fattyacid such as a zinc salt or a magnesium salt of an unsaturated fattyacid having 3 to 8 carbon atoms such as acrylic or methacrylic acid.Suitable cross linking agents include metal salt diacrylates,dimethacrylates and monomethacrylates wherein the metal is magnesium,calcium, zinc, aluminum, sodium, lithium or nickel. The crosslinkingagent is present in an amount from about 15 to about 40 parts perhundred of the rubber, preferably in an amount from about 19 to about 25parts per hundred of the rubber and most preferably having about 20 to24 parts crosslinking agent per hundred of rubber. The core compositionsof the present invention may also include at least one organic orinorganic cis-trans catalyst to convert a portion of the cis-isomer ofpolybutadiene to the trans-isomer, as desired.

The initiator agent can be any known polymerization initiator whichdecomposes during the cure cycle. Suitable initiators include peroxidecompounds such as dicumyl peroxide, 1,1-di-(t-butylperoxy)3,3,5-trimethyl cyclohexane, a-a bis-(t-butylperoxy) diisopropylbenzene,2,5-dimethyl-2,5di-(t-butylperoxy) hexane or di-t-butyl peroxide andmixtures thereof.

Fillers, any compound or composition that can be used to vary thedensity and other properties of the core, typically include materialssuch as tungsten, zinc oxide, barium sulfate, silica, calcium carbonate,zinc carbonate, metals, metal oxides and salts, regrind (recycled corematerial typically ground to about 30 mesh particle),high-Mooney-viscosity rubber regrind, and the like.

The HNP compositions of the present invention may also be moistureresistant. For purposes of the present disclosure, a composition is“moisture resistant” if it has a moisture vapor transmission rate(“MVTR”) of 12.5 gmil/100 in²/day or less. Preferably, the moistureresistant compositions of the present invention have an MVTR of 8.0gmil/100 in²/day or less, or 6.5 gmil/100 in²/day or less, or 5.0gmil/100 in²/day or less, or 4.0 gmil/100 in²/day or less, or 2.5gmil/100 in²/day or less, or 2.0 gmil/100 in²/day or less. As usedherein, moisture vapor transmission rate (MVTR) is given in gmil/100in²/day, and is measured at 20° C., and according to ASTM F 1249-99.

In a particular embodiment, the cation source is selected from metalions and compounds of calcium, metal ions and compounds of zinc, andcombinations thereof. In a particular aspect of this embodiment, theequivalent percentage of calcium and/or zinc salt(s) in the finalcomposition is 50% or higher, or 60% or higher, or 70% or higher, or 80%or higher, or 90% or higher, based on the total salts present in thefinal composition, wherein the equivalent % is determined by multiplyingthe mol % of the cation by the valence of the cation. In anotherparticular embodiment, the cation source is selected from metal ions andcompounds of lithium, sodium, potassium, magnesium, calcium, zinc, andcombinations thereof. In another particular embodiment, the cationsource is selected from metal ions and compounds of lithium, metal ionsand compounds of zinc, and combinations thereof. Suitable cation sourcesalso include mixtures of lithium and/or zinc cations with other cations.Other cations suitable for mixing with lithium and/or zinc cations toproduce the HNP include, but are not limited to, the “less hydrophilic”cations disclosed in U.S. Patent Application Publication No.2006/0106175; conventional HNP cations, such as those disclosed in U.S.Pat. Nos. 6,756,436 and 6,824,477; and the cations disclosed in U.S.Patent Application Publication No. 2005/0267240. The entire disclosureof each of these references is hereby incorporated herein by reference.In a particular aspect of this embodiment, the percentage of lithiumand/or zinc salts in the composition is preferably 50% or higher, or 55%or higher, or 60% or higher, or 65% or higher, or 70% or higher, or 80%or higher, or 90% or higher, or 95% or higher, or 100%, based on thetotal salts present in the composition. The amount of cation source usedis readily determined based on the desired level of neutralization.

The golf ball cores of the present invention may also comprise a varietyof constructions. For example, the core may comprise a single layer or aplurality of layers. The core may also comprise a layer of tensionedelastomeric material. In another embodiment of the present invention,golf ball comprises a solid center surrounded by at least one additionalsolid outer core layer. The “dual” core is surrounded by a “double”cover comprising an inner cover layer and an outer cover layer.

Preferably, the solid center comprises the HNP's of the presentinvention. In another embodiment, the inner cover layer comprises thehighly-neutralized acid copolymers of the present invention. In analternative embodiment, the outer core layer comprises thehighly-neutralized acid copolymers of the present invention.

At least one of the outer core layers is formed of a resilientrubber-based component comprising a high-Mooney-viscosity rubber, and acrosslinking agent present in an amount from about 20 to about 40 partsper hundred, from about 30 to about 38 parts per hundred, and mostpreferably about 37 parts per hundred. It should be understood that theterm “parts per hundred” is with reference to the rubber by weight.

When the golf ball of the present invention includes an intermediatelayer, such as an outer core layer or an inner cover layer, any or allof these layer(s) may comprise thermoplastic and thermosetting material,but preferably the intermediate layer(s), if present, comprise anysuitable material, such as ionic copolymers of ethylene and anunsaturated monocarboxylic acid which are available under the trademarkSURLYN® of E.I. DuPont de Nemours & Co., of Wilmington, Del., or IOTEK®or ESCOR® of Exxon. These are copolymers or terpolymers of ethylene andmethacrylic acid or acrylic acid partially neutralized with salts ofzinc, sodium, lithium, magnesium, potassium, calcium, manganese, nickelor the like, in which the salts are the reaction product of an olefinhaving from 2 to 8 carbon atoms and an unsaturated monocarboxylic acidhaving 3 to 8 carbon atoms. The carboxylic acid groups of the copolymermay be totally or partially neutralized and might include methacrylic,crotonic, maleic, fumaric or itaconic acid.

This golf ball can likewise include one or more homopolymeric orcopolymeric inner cover materials, such as:

-   -   (1) Vinyl resins, such as those formed by the polymerization of        vinyl chloride, or by the copolymerization of vinyl chloride        with vinyl acetate, acrylic esters or vinylidene chloride;    -   (2) Polyolefins, such as polyethylene, polypropylene,        polybutylene and copolymers such as ethylene methylacrylate,        ethylene ethylacrylate, ethylene vinyl acetate, ethylene        methacrylic or ethylene acrylic acid or propylene acrylic acid        and copolymers and homopolymers produced using a single-site        catalyst or a metallocene catalyst;    -   (3) Polyurethanes, such as those prepared from polyols and        diisocyanates or polyisocyanates, in particular PPDI-based        thermoplastic polyurethanes, and those disclosed in U.S. Pat.        No. 5,334,673;    -   (4) Polyureas, such as those disclosed in U.S. Pat. No.        5,484,870;    -   (5) Polyamides, such as poly(hexamethylene adipamide) and others        prepared from diamines and dibasic acids, as well as those from        amino acids such as poly(caprolactam), and blends of polyamides        with SURLYN®, polyethylene, ethylene copolymers,        ethylene-propylene-non-conjugated diene terpolymer, and the        like;    -   (6) Acrylic resins and blends of these resins with poly vinyl        chloride, elastomers, and the like;    -   (7) Thermoplastics, such as urethane; olefinic thermoplastic        rubbers, such as blends of polyolefins with        ethylene-propylene-non-conjugated diene terpolymer; block        copolymers of styrene and butadiene, isoprene or        ethylene-butylene rubber; or copoly(ether-amide), such as        PEBAX®, sold by ELF Atochem of Philadelphia, Pa.;    -   (8) Polyphenylene oxide resins or blends of polyphenylene oxide        with high impact polystyrene as sold under the trademark NORYL®        by General Electric Company of Pittsfield, Mass.;    -   (9) Thermoplastic polyesters, such as polyethylene        terephthalate, polybutylene terephthalate, polyethylene        terephthalate/glycol modified, poly(trimethylene terepthalate),        and elastomers sold under the trademarks HYTREL® by E.I. DuPont        de Nemours & Co. of Wilmington, Del., and LOMOD® by General        Electric Company of Pittsfield, Mass.;    -   (10) Blends and alloys, including polycarbonate with        acrylonitrile butadiene styrene, polybutylene terephthalate,        polyethylene terephthalate, styrene maleic anhydride,        polyethylene, elastomers, and the like, and polyvinyl chloride        with acrylonitrile butadiene styrene or ethylene vinyl acetate        or other elastomers; and    -   (11) Blends of thermoplastic rubbers with polyethylene,        propylene, polyacetal, nylon, polyesters, cellulose esters, and        the like.

Preferably, the inner cover includes polymers, such as ethylene,propylene, butene-1 or hexane-1 based homopolymers or copolymersincluding functional monomers, such as acrylic and methacrylic acid andfully or partially neutralized ionomer resins and their blends, methylacrylate, methyl methacrylate homopolymers and copolymers, imidized,amino group containing polymers, polycarbonate, reinforced polyamides,polyphenylene oxide, high impact polystyrene, polyether ketone,polysulfone, poly(phenylene sulfide), acrylonitrile-butadiene,acrylic-styrene-acrylonitrile, poly(ethylene terephthalate),poly(butylene terephthalate), poly(vinyl alcohol),poly(tetrafluoroethylene) and their copolymers including functionalcomonomers, and blends thereof. Suitable cover compositions also includea polyether or polyester thermoplastic urethane, a thermosetpolyurethane, a low modulus ionomer, such as acid-containing ethylenecopolymer ionomers, including E/X/Y terpolymers where E is ethylene, Xis an acrylate or methacrylate-based softening comonomer present inabout 0 to 50 weight percent and Y is acrylic or methacrylic acidpresent in about 5 to 35 weight percent. More preferably, in a low spinrate embodiment designed for maximum distance, the acrylic ormethacrylic acid is present in about 16 to 35 weight percent, making theionomer a high modulus ionomer. In a higher spin embodiment, the innercover layer includes an ionomer where an acid is present in about 10 to15 weight percent and includes a softening comonomer. Additionally,high-density polyethylene (“HDPE”), low-density polyethylene (“LDPE”),LLDPE, and homo- and co-polymers of polyolefin are suitable for avariety of golf ball layers.

In one embodiment, the outer cover preferably includes a polyurethanecomposition comprising the reaction product of at least onepolyisocyanate, polyol, and at least one curing agent. Anypolyisocyanate available to one of ordinary skill in the art is suitablefor use according to the invention. Exemplary polyisocyanates include,but are not limited to, 4,4′-diphenylmethane diisocyanate (“MDI”);polymeric MDI; carbodiimide-modified liquid MDI;4,4′-dicyclohexylmethane diisocyanate (“H₁₂MDI”); p-phenylenediisocyanate (“PPDI”); m-phenylene diisocyanate (“MPDI”); toluenediisocyanate (“TDI”); 3,3′-dimethyl-4,4′-biphenylene diisocyanate(“TODI”); isophoronediisocyanate (“IPDI”); hexamethylene diisocyanate(“HDI”); naphthalene diisocyanate (“NDI”); xylene diisocyanate (“XDI”);p-tetramethylxylene diisocyanate (“p-TMXDI”); m-tetramethylxylenediisocyanate (“m-TMXDI”); ethylene diisocyanate;propylene-1,2-diisocyanate; tetramethylene-1,4-diisocyanate; cyclohexyldiisocyanate; 1,6-hexamethylene-diisocyanate (“HDI”);dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; methylcyclohexylene diisocyanate; triisocyanate of HDI; triisocyanate of2,4,4-trimethyl-1,6-hexane diisocyanate (“TMDI”); tetracenediisocyanate; napthalene diisocyanate; anthracene diisocyanate;isocyanurate of toluene diisocyanate; uretdione of hexamethylenediisocyanate; and mixtures thereof. Polyisocyanates are known to thoseof ordinary skill in the art as having more than one isocyanate group,e.g., di-isocyanate, tri-isocyanate, and tetra-isocyanate. Preferably,the polyisocyanate includes MDI, PPDI, TDI, or a mixture thereof, andmore preferably, the polyisocyanate includes MDI. It should beunderstood that, as used herein, the term “MDI” includes4,4′-diphenylmethane diisocyanate, polymeric MDI, carbodiimide-modifiedliquid MDI, and mixtures thereof and, additionally, that thediisocyanate employed may be “low free monomer,” understood by one ofordinary skill in the art to have lower levels of “free” monomerisocyanate groups, typically less than about 0.1% free monomer groups.Examples of “low free monomer” diisocyanates include, but are notlimited to Low Free Monomer MDI, Low Free Monomer TDI, and Low FreeMonomer PPDI.

The at least one polyisocyanate should have less than about 14%unreacted NCO groups. Preferably, the at least one polyisocyanate has nogreater than about 7.5% NCO, and more preferably, less than about 7.0%.

Any polyol available to one of ordinary skill in the art is suitable foruse according to the invention. Exemplary polyols include, but are notlimited to, polyether polyols, hydroxy-terminated polybutadiene(including partially/fully hydrogenated derivatives), polyester polyols,polycaprolactone polyols, and polycarbonate polyols. In one preferredembodiment, the polyol includes polyether polyol. Examples include, butare not limited to, polytetramethylene ether glycol (“PTMEG”),polyethylene propylene glycol, polyoxypropylene glycol, and mixturesthereof. The hydrocarbon chain can have saturated or unsaturated bondsand substituted or unsubstituted aromatic and cyclic groups. Preferably,the polyol of the present invention includes PTMEG.

In another embodiment, polyester polyols are included in thepolyurethane material of the invention. Suitable polyester polyolsinclude, but are not limited to, polyethylene adipate glycol;polybutylene adipate glycol; polyethylene propylene adipate glycol;o-phthalate-1,6-hexanediol; poly(hexamethylene adipate) glycol; andmixtures thereof. The hydrocarbon chain can have saturated orunsaturated bonds, or substituted or unsubstituted aromatic and cyclicgroups.

In another embodiment, polycaprolactone polyols are included in thematerials of the invention. Suitable polycaprolactone polyols include,but are not limited to, 1,6-hexanediol-initiated polycaprolactone,diethylene glycol initiated polycaprolactone, trimethylol propaneinitiated polycaprolactone, neopentyl glycol initiated polycaprolactone,1,4-butanediol-initiated polycaprolactone, and mixtures thereof. Thehydrocarbon chain can have saturated or unsaturated bonds, orsubstituted or unsubstituted aromatic and cyclic groups.

In yet another embodiment, the polycarbonate polyols are included in thepolyurethane material of the invention. Suitable polycarbonates include,but are not limited to, polyphthalate carbonate and poly(hexamethylenecarbonate) glycol. The hydrocarbon chain can have saturated orunsaturated bonds, or substituted or unsubstituted aromatic and cyclicgroups. In one embodiment, the molecular weight of the polyol is fromabout 200 to about 4000.

Polyamine curatives are also suitable for use in the polyurethanecomposition of the invention and have been found to improve cut, shear,and impact resistance of the resultant balls. Preferred polyaminecuratives include, but are not limited to,3,5-dimethylthio-2,4-toluenediamine and isomers thereof;3,5-diethyltoluene-2,4-diamine and isomers thereof, such as3,5-diethyltoluene-2,6-diamine;4,4′-bis-(sec-butylamino)-diphenylmethane;1,4-bis-(sec-butylamino)-benzene, 4,4′-methylene-bis-(2-chloroaniline);4,4′-methylene-bis-(3-chloro-2,6-diethylaniline) (“MCDEA”);polytetramethyleneoxide-di-p-aminobenzoate; N,N′-dialkyldiamino diphenylmethane; p,p′-methylene dianiline (“MDA”); m-phenylenediamine (“MPDA”);4,4′-methylene-bis-(2-chloroaniline) (“MOCA”);4,4′-methylene-bis-(2,6-diethylaniline) (“MDEA”);4,4′-methylene-bis-(2,3-dichloroaniline) (“MDCA”);4,4′-diamino-3,3′-diethyl-5,5′-dimethyl diphenylmethane;2,2′,3,3′-tetrachloro diamino diphenylmethane; trimethylene glycoldi-p-aminobenzoate; and mixtures thereof. Preferably, the curing agentof the present invention includes 3,5-dimethylthio-2,4-toluenediamineand isomers thereof, such as ETHACURE 300, commercially available fromAlbermarle Corporation of Baton Rouge, La. Suitable polyamine curatives,which include both primary and secondary amines, preferably havemolecular weights ranging from about 64 to about 2000.

At least one of a diol, triol, tetraol, or hydroxy-terminated curativesmay be added to the aforementioned polyurethane composition. Suitablediol, triol, and tetraol groups include ethylene glycol; diethyleneglycol; polyethylene glycol; propylene glycol; polypropylene glycol;lower molecular weight polytetramethylene ether glycol;1,3-bis(2-hydroxyethoxy) benzene;1,3-bis-[2-(2-hydroxyethoxy)ethoxy]benzene;1,3-bis-{2-[2-(2-hydroxyethoxy) ethoxy]ethoxy}benzene; 1,4-butanediol;1,5-pentanediol; 1,6-hexanediol; resorcinol-di-(β-hydroxyethyl)ether;hydroquinone-di-(β-hydroxyethyl)ether; and mixtures thereof. Preferredhydroxy-terminated curatives include 1,3-bis(2-hydroxyethoxy) benzene;1,3-bis-[2-(2-hydroxyethoxy) ethoxy]benzene;1,3-bis-{2-[2-(2-hydroxyethoxy) ethoxy]ethoxy}benzene; 1,4-butanediol,and mixtures thereof. Preferably, the hydroxy-terminated curatives havemolecular weights ranging from about 48 to 2000. It should be understoodthat molecular weight, as used herein, is the absolute weight averagemolecular weight and would be understood as such by one of ordinaryskill in the art.

Both the hydroxy-terminated and amine curatives can include one or moresaturated, unsaturated, aromatic, and cyclic groups. Additionally, thehydroxy-terminated and amine curatives can include one or more halogengroups. The polyurethane composition can be formed with a blend ormixture of curing agents. If desired, however, the polyurethanecomposition may be formed with a single curing agent.

In a preferred embodiment of the present invention, saturatedpolyurethanes used to form cover layers, preferably the outer coverlayer, and may be selected from among both castable thermoset andthermoplastic polyurethanes.

In this embodiment, the saturated polyurethanes of the present inventionare substantially free of aromatic groups or moieties. Saturatedpolyurethanes suitable for use in the invention are a product of areaction between at least one polyurethane prepolymer and at least onesaturated curing agent. The polyurethane prepolymer is a product formedby a reaction between at least one saturated polyol and at least onesaturated diisocyanate. As is well known in the art, a catalyst may beemployed to promote the reaction between the curing agent and theisocyanate and polyol.

Saturated diisocyanates which can be used include, without limitation,ethylene diisocyanate; propylene-1,2-diisocyanate;tetramethylene-1,4-diisocyanate; 1,6-hexamethylene-diisocyanate (“HDI”);2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylenediisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethanediisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; isophoronediisocyanate (“IPDI”); methyl cyclohexylene diisocyanate; triisocyanateof HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexane diisocyanate(“TMDI”). The most preferred saturated diisocyanates are4,4′-dicyclohexylmethane diisocyanate (“HMDI”) and isophoronediisocyanate (“IPDI”).

Saturated polyols which are appropriate for use in this inventioninclude without limitation polyether polyols such as polytetramethyleneether glycol and poly(oxypropylene) glycol. Suitable saturated polyesterpolyols include polyethylene adipate glycol, polyethylene propyleneadipate glycol, polybutylene adipate glycol, polycarbonate polyol andethylene oxide-capped polyoxypropylene diols. Saturated polycaprolactonepolyols which are useful in the invention include diethyleneglycol-initiated polycaprolactone, 1,4-butanediol-initiatedpolycaprolactone, 1,6-hexanediol-initiated polycaprolactone; trimethylolpropane-initiated polycaprolactone, neopentyl glycol initiatedpolycaprolactone, and polytetramethylene ether glycol-initiatedpolycaprolactone. The most preferred saturated polyols arepolytetramethylene ether glycol and PTMEG-initiated polycaprolactone.

Suitable saturated curatives include 1,4-butanediol, ethylene glycol,diethylene glycol, polytetramethylene ether glycol, propylene glycol;trimethanolpropane; tetra-(2-hydroxypropyl)-ethylenediamine; isomers andmixtures of isomers of cyclohexyldimethylol, isomers and mixtures ofisomers of cyclohexane bis(methylamine); triisopropanolamine; ethylenediamine; diethylene triamine; triethylene tetramine; tetraethylenepentamine; 4,4′-dicyclohexylmethane diamine;2,2,4-trimethyl-1,6-hexanediamine; 2,4,4-trimethyl-1,6-hexanediamine;diethyleneglycol di-(aminopropyl)ether;4,4′-bis-(sec-butylamino)-dicyclohexylmethane;1,2-bis-(sec-butylamino)cyclohexane; 1,4-bis-(sec-butylamino)cyclohexane; isophorone diamine; hexamethylene diamine; propylenediamine; 1-methyl-2,4-cyclohexyl diamine; 1-methyl-2,6-cyclohexyldiamine; 1,3-diaminopropane; dimethylamino propylamine; diethylaminopropylamine; imido-bis-propylamine; isomers and mixtures of isomers ofdiaminocyclohexane; monoethanolamine; diethanolamine; triethanolamine;monoisopropanolamine; and diisopropanolamine. The most preferredsaturated curatives are 1,4-butanediol, 1,4-cyclohexyldimethylol and4,4′-bis-(sec-butylamino)-dicyclohexylmethane.

The compositions of the invention may also be polyurea-based, which aredistinctly different from polyurethane compositions, but also result indesirable aerodynamic and aesthetic characteristics when used in golfball components. The polyurea-based compositions are preferablysaturated in nature.

Without being bound to any particular theory, it is now believed thatsubstitution of the long chain polyol segment in the polyurethaneprepolymer with a long chain polyamine oligomer soft segment to form apolyurea prepolymer, improves shear, cut, and resiliency, as well asadhesion to other components. Thus, the polyurea compositions of thisinvention may be formed from the reaction product of an isocyanate andpolyamine prepolymer crosslinked with a curing agent. For example,polyurea-based compositions of the invention may be prepared from atleast one isocyanate, at least one polyether amine, and at least onediol curing agent or at least one diamine curing agent.

Any polyamine available to one of ordinary skill in the art is suitablefor use in the polyurea prepolymer. Polyether amines are particularlysuitable for use in the prepolymer. As used herein, “polyether amines”refer to at least polyoxyalkyleneamines containing primary amino groupsattached to the terminus of a polyether backbone. Due to the rapidreaction of isocyanate and amine, and the insolubility of many ureaproducts, however, the selection of diamines and polyether amines islimited to those allowing the successful formation of the polyureaprepolymers. In one embodiment, the polyether backbone is based ontetramethylene, propylene, ethylene, trimethylolpropane, glycerin, andmixtures thereof.

Suitable polyether amines include, but are not limited to,methyldiethanolamine; polyoxyalkylenediamines such as,polytetramethylene ether diamines, polyoxypropylenetriamine, andpolyoxypropylene diamines; poly(ethylene oxide capped oxypropylene)ether diamines; propylene oxide-based triamines;triethyleneglycoldiamines; trimethylolpropane-based triamines;glycerin-based triamines; and mixtures thereof. In one embodiment, thepolyether amine used to form the prepolymer is JEFFAMINE® D2000(manufactured by Huntsman Chemical Co. of Austin, Tex.).

The molecular weight of the polyether amine for use in the polyureaprepolymer may range from about 100 to about 5000. As used herein, theterm “about” is used in connection with one or more numbers or numericalranges, should be understood to refer to all such numbers, including allnumbers in a range. In one embodiment, the polyether amine molecularweight is about 200 or greater, preferably about 230 or greater. Inanother embodiment, the molecular weight of the polyether amine is about4000 or less. In yet another embodiment, the molecular weight of thepolyether amine is about 600 or greater. In still another embodiment,the molecular weight of the polyether amine is about 3000 or less. Inyet another embodiment, the molecular weight of the polyether amine isbetween about 1000 and about 3000, and more preferably is between about1500 to about 2500. Because lower molecular weight polyether amines maybe prone to forming solid polyureas, a higher molecular weight oligomer,such as Jeffamine D2000, is preferred.

In one embodiment, the polyether amine has the generic structure:

wherein the repeating unit x has a value ranging from about 1 to about70. Even more preferably, the repeating unit may be from about 5 toabout 50, and even more preferably is from about 12 to about 35.

In another embodiment, the polyether amine has the generic structure:

wherein the repeating units x and z have combined values from about 3.6to about 8 and the repeating unit y has a value ranging from about 9 toabout 50, and wherein R is —(CH₂)_(a)—, where “a” may be a repeatingunit ranging from about 1 to about 10.

In yet another embodiment, the polyether amine has the genericstructure:

H₂N—(R)—O—(R)—O—(R)—NH₂

wherein R is —(CH₂)_(a)—, and “a” may be a repeating unit ranging fromabout 1 to about 10.

As briefly discussed above, some amines may be unsuitable for reactionwith the isocyanate because of the rapid reaction between the twocomponents. In particular, shorter chain amines are fast reacting. Inone embodiment, however, a hindered secondary diamine may be suitablefor use in the prepolymer. Without being bound to any particular theory,it is believed that an amine with a high level of stearic hindrance,e.g., a tertiary butyl group on the nitrogen atom, has a slower reactionrate than an amine with no hindrance or a low level of hindrance. Forexample, 4,4′-bis-(sec-butylamino)-dicyclohexylmethane (CLEARLINK® 1000)may be suitable for use in combination with an isocyanate to form thepolyurea prepolymer.

Any isocyanate available to one of ordinary skill in the art is suitablefor use in the polyurea prepolymer. Isocyanates for use with the presentinvention include aliphatic, cycloaliphatic, araliphatic, aromatic, anyderivatives thereof, and combinations of these compounds having two ormore isocyanate (NCO) groups per molecule. The isocyanates may beorganic polyisocyanate-terminated prepolymers. The isocyanate-containingreactable component may also include any isocyanate-functional monomer,dimer, trimer, or multimeric adduct thereof, prepolymer,quasi-prepolymer, or mixtures thereof. Isocyanate-functional compoundsmay include monoisocyanates or polyisocyanates that include anyisocyanate functionality of two or more.

Suitable isocyanate-containing components include diisocyanates havingthe generic structure: O═C═N—R—N═C═O, where R is preferably a cyclic,aromatic, or linear or branched hydrocarbon moiety containing from about1 to about 20 carbon atoms. The diisocyanate may also contain one ormore cyclic groups or one or more phenyl groups. When multiple cyclic oraromatic groups are present, linear and/or branched hydrocarbonscontaining from about 1 to about 10 carbon atoms can be present asspacers between the cyclic or aromatic groups. In some cases, the cyclicor aromatic group(s) may be substituted at the 2-, 3-, and/or4-positions, or at the ortho-, meta-, and/or para-positions,respectively. Substituted groups may include, but are not limited to,halogens, primary, secondary, or tertiary hydrocarbon groups, or amixture thereof.

Examples of diisocyanates that can be used with the present inventioninclude, but are not limited to, substituted and isomeric mixturesincluding 2,2′-, 2,4′-, and 4,4′-diphenylmethane diisocyanate (MDI);3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI); toluene diisocyanate(TDI); polymeric MDI; carbodiimide-modified liquid 4,4′-diphenylmethanediisocyanate; para-phenylene diisocyanate (PPDI); meta-phenylenediisocyanate (MPDI); triphenyl methane-4,4′- and triphenylmethane-4,4′-triisocyanate; naphthylene-1,5-diisocyanate; 2,4′-, 4,4′-,and 2,2-biphenyl diisocyanate; polyphenyl polymethylene polyisocyanate(PMDI); mixtures of MDI and PMDI; mixtures of PMDI and TDI; ethylenediisocyanate; propylene-1,2-diisocyanate;tetramethylene-1,2-diisocyanate; tetramethylene-1,3-diisocyanate;tetramethylene-1,4-diisocyanate; 1,6-hexamethylene-diisocyanate (HDI);octamethylene diisocyanate; decamethylene diisocyanate;2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylenediisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate;cyclohexane-1,4-diisocyanate; methyl-cyclohexylene diisocyanate (HTDI);2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate;4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate;1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexanediisocyanate; 4,4′-bis(isocyanatomethyl) dicyclohexane;2,4′-bis(isocyanatomethyl) dicyclohexane; isophorone diisocyanate(IPDI); triisocyanate of HDI; triisocyanate of2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI); 4,4′-dicyclohexylmethanediisocyanate (H₁₂MDI); 2,4-hexahydrotoluene diisocyanate;2,6-hexahydrotoluene diisocyanate; 1,2-, 1,3-, and 1,4-phenylenediisocyanate; aromatic aliphatic isocyanate, such as 1,2-, 1,3-, and1,4-xylene diisocyanate; meta-tetramethylxylene diisocyanate (m-TMXDI);para-tetramethylxylene diisocyanate (p-TMXDI); trimerized isocyanurateof any polyisocyanate, such as isocyanurate of toluene diisocyanate,trimer of diphenylmethane diisocyanate, trimer of tetramethylxylenediisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurateof isophorone diisocyanate, and mixtures thereof; dimerized uredione ofany polyisocyanate, such as uretdione of toluene diisocyanate, uretdioneof hexamethylene diisocyanate, and mixtures thereof; modifiedpolyisocyanate derived from the above isocyanates and polyisocyanates;and mixtures thereof.

Examples of saturated diisocyanates that can be used with the presentinvention include, but are not limited to, ethylene diisocyanate;propylene-1,2-diisocyanate; tetramethylene diisocyanate;tetramethylene-1,4-diisocyanate; 1,6-hexamethylene-diisocyanate (HDI);octamethylene diisocyanate; decamethylene diisocyanate;2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylenediisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate;cyclohexane-1,4-diisocyanate; methyl-cyclohexylene diisocyanate (HTDI);2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate;4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate;1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexanediisocyanate; 4,4′-bis(isocyanatomethyl) dicyclohexane;2,4′-bis(isocyanatomethyl) dicyclohexane; isophorone diisocyanate(IPDI); triisocyanate of HDI; triisocyanate of2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI); 4,4′-dicyclohexylmethanediisocyanate (H₁₂MDI); 2,4-hexahydrotoluene diisocyanate;2,6-hexahydrotoluene diisocyanate; and mixtures thereof. Aromaticaliphatic isocyanates may also be used to form light stable materials.Examples of such isocyanates include 1,2-, 1,3-, and 1,4-xylenediisocyanate; meta-tetramethylxylene diisocyanate (m-TMXDI);para-tetramethylxylene diisocyanate (p-TMXDI); trimerized isocyanurateof any polyisocyanate, such as isocyanurate of toluene diisocyanate,trimer of diphenylmethane diisocyanate, trimer of tetramethylxylenediisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurateof isophorone diisocyanate, and mixtures thereof; dimerized uredione ofany polyisocyanate, such as uretdione of toluene diisocyanate, uretdioneof hexamethylene diisocyanate, and mixtures thereof; modifiedpolyisocyanate derived from the above isocyanates and polyisocyanates;and mixtures thereof. In addition, the aromatic aliphatic isocyanatesmay be mixed with any of the saturated isocyanates listed above for thepurposes of this invention.

The number of unreacted NCO groups in the polyurea prepolymer ofisocyanate and polyether amine may be varied to control such factors asthe speed of the reaction, the resultant hardness of the composition,and the like. For instance, the number of unreacted NCO groups in thepolyurea prepolymer of isocyanate and polyether amine may be less thanabout 14 percent. In one embodiment, the polyurea prepolymer has fromabout 5 percent to about 11 percent unreacted NCO groups, and even morepreferably has from about 6 to about 9.5 percent unreacted NCO groups.In one embodiment, the percentage of unreacted NCO groups is about 3percent to about 9 percent. Alternatively, the percentage of unreactedNCO groups in the polyurea prepolymer may be about 7.5 percent or less,and more preferably, about 7 percent or less. In another embodiment, theunreacted NCO content is from about 2.5 percent to about 7.5 percent,and more preferably from about 4 percent to about 6.5 percent.

When formed, polyurea prepolymers may contain about 10 percent to about20 percent by weight of the prepolymer of free isocyanate monomer. Thus,in one embodiment, the polyurea prepolymer may be stripped of the freeisocyanate monomer. For example, after stripping, the prepolymer maycontain about 1 percent or less free isocyanate monomer. In anotherembodiment, the prepolymer contains about 0.5 percent by weight or lessof free isocyanate monomer.

The polyether amine may be blended with additional polyols to formulatecopolymers that are reacted with excess isocyanate to form the polyureaprepolymer. In one embodiment, less than about 30 percent polyol byweight of the copolymer is blended with the saturated polyether amine.In another embodiment, less than about 20 percent polyol by weight ofthe copolymer, preferably less than about 15 percent by weight of thecopolymer, is blended with the polyether amine. The polyols listed abovewith respect to the polyurethane prepolymer, e.g., polyether polyols,polycaprolactone polyols, polyester polyols, polycarbonate polyols,hydrocarbon polyols, other polyols, and mixtures thereof, are alsosuitable for blending with the polyether amine. The molecular weight ofthese polymers may be from about 200 to about 4000, but also may be fromabout 1000 to about 3000, and more preferably are from about 1500 toabout 2500.

The polyurea composition can be formed by crosslinking the polyureaprepolymer with a single curing agent or a blend of curing agents. Thecuring agent of the invention is preferably an amine-terminated curingagent, more preferably a secondary diamine curing agent so that thecomposition contains only urea linkages. In one embodiment, theamine-terminated curing agent may have a molecular weight of about 64 orgreater. In another embodiment, the molecular weight of the amine-curingagent is about 2000 or less. As discussed above, certainamine-terminated curing agents may be modified with a compatibleamine-terminated freezing point depressing agent or mixture ofcompatible freezing point depressing agents.

Suitable amine-terminated curing agents include, but are not limited to,ethylene diamine; hexamethylene diamine; 1-methyl-2,6-cyclohexyldiamine; tetrahydroxypropylene ethylene diamine; 2,2,4- and2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; derivatives of4,4′-bis-(sec-butylamino)-dicyclohexylmethane; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis-(methylamine);1,3-cyclohexane-bis-(methylamine); diethylene glycoldi-(aminopropyl)ether; 2-methylpentamethylene-diamine;diaminocyclohexane; diethylene triamine; triethylene tetramine;tetraethylene pentamine; propylene diamine; 1,3-diaminopropane;dimethylamino propylamine; diethylamino propylamine; dipropylenetriamine; imido-bis-propylamine; monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;isophoronediamine; 4,4′-methylenebis-(2-chloroaniline);3,5;dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; 3,5-diethylthio-2,4-toluenediamine;3,5;diethylthio-2,6-toluenediamine;4,4′-bis-(sec-butylamino)-diphenylmethane and derivatives thereof;1,4-bis-(sec-butylamino)-benzene; 1,2-bis-(sec-butylamino)-benzene;N,N′-dialkylamino-diphenylmethane; N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylene diamine;trimethyleneglycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate;4,4′-methylenebis-(3-chloro-2,6-diethyleneaniline);4,4′-methylenebis-(2,6-diethylaniline); meta-phenylenediamine;paraphenylenediamine; and mixtures thereof. In one embodiment, theamine-terminated curing agent is4,4′-bis-(sec-butylamino)-dicyclohexylmethane.

Suitable saturated amine-terminated curing agents include, but are notlimited to, ethylene diamine; hexamethylene diamine;1-methyl-2,6-cyclohexyl diamine; tetrahydroxypropylene ethylene diamine;2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; derivatives of4,4′-bis-(sec-butylamino)-dicyclohexylmethane; 4,4′-dicyclohexylmethanediamine; 4,4′-methylenebis-(2,6-diethylaminocyclohexane;1,4-cyclohexane-bis-(methylamine); 1,3-cyclohexane-bis-(methylamine);diethylene glycol di-(aminopropyl)ether; 2-methylpentamethylene-diamine;diaminocyclohexane; diethylene triamine; triethylene tetramine;tetraethylene pentamine; propylene diamine; 1,3-diaminopropane;dimethylamino propylamine; diethylamino propylamine;imido-bis-propylamine; monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;isophoronediamine; triisopropanolamine; and mixtures thereof. Inaddition, any of the polyether amines listed above may be used as curingagents to react with the polyurea prepolymers.

Suitable catalysts include, but are not limited to bismuth catalyst,oleic acid, triethylenediamine (DABCO®-33LV), di-butyltin dilaurate(DABCO®-T12) and acetic acid. The most preferred catalyst is di-butyltindilaurate (DABCO®-T12). DABCO® materials are manufactured by AirProducts and Chemicals, Inc.

Thermoplastic materials may be blended with other thermoplasticmaterials, but thermosetting materials are difficult if not impossibleto blend homogeneously after the thermosetting materials are formed.Preferably, the saturated polyurethane comprises from about 1% to about100%, more preferably from about 10% to about 75% of the covercomposition and/or the intermediate layer composition. About 90% toabout 10%, more preferably from about 90% to about 25% of the coverand/or the intermediate layer composition is comprised of one or moreother polymers and/or other materials as described below. Such polymersinclude, but are not limited to polyurethane/polyurea ionomers,polyurethanes or polyureas, epoxy resins, polyethylenes, polyamides andpolyesters, polycarbonates and polyacrylin. Unless otherwise statedherein, all percentages are given in percent by weight of the totalcomposition of the golf ball layer in question.

Polyurethane prepolymers are produced by combining at least one polyol,such as a polyether, polycaprolactone, polycarbonate or a polyester, andat least one isocyanate. Thermosetting polyurethanes are obtained bycuring at least one polyurethane prepolymer with a curing agent selectedfrom a polyamine, triol or tetraol. Thermoplastic polyurethanes areobtained by curing at least one polyurethane prepolymer with a diolcuring agent. The choice of the curatives is critical because someurethane elastomers that are cured with a diol and/or blends of diols donot produce urethane elastomers with the impact resistance required in agolf ball cover. Blending the polyamine curatives with diol curedurethane elastomeric formulations leads to the production of thermoseturethanes with improved impact and cut resistance.

Thermoplastic polyurethanes may be blended with suitable materials toproduce a thermoplastic end product. Examples of such additionalmaterials may include ionomers such as the SURLYN®, ESCOR® and IOTEK®copolymers described above.

Other suitable materials which may be combined with the saturatedpolyurethanes in forming the cover and/or intermediate layer(s) of thegolf balls of the invention include ionic or non-ionic polyurethanes andpolyureas, epoxy resins, polyethylenes, polyamides and polyesters. Forexample, the cover and/or intermediate layer may be formed from a blendof at least one saturated polyurethane and thermoplastic or thermosetionic and non-ionic urethanes and polyurethanes, cationic urethaneionomers and urethane epoxies, ionic and non-ionic polyureas and blendsthereof. Examples of suitable urethane ionomers are disclosed in U.S.Pat. No. 5,692,974 entitled “Golf Ball Covers”, the disclosure of whichis hereby incorporated by reference in its entirety. Other examples ofsuitable polyurethanes are described in U.S. Pat. No. 5,334,673.Examples of appropriate polyureas are discussed in U.S. Pat. No.5,484,870 and examples of suitable polyurethanes cured with epoxy groupcontaining curing agents are disclosed in U.S. Pat. No. 5,908,358, thedisclosures of which are hereby incorporated herein by reference intheir entirety.

A variety of conventional components can be added to the covercompositions of the present invention. These include, but are notlimited to, white pigment such as TiO₂, ZnO, optical brighteners,surfactants, processing aids, foaming agents, density-controllingfillers, UV stabilizers and light stabilizers. Saturated polyurethanesare resistant to discoloration. However, they are not immune todeterioration in their mechanical properties upon weathering. Additionof UV absorbers and light stabilizers therefore helps to maintain thetensile strength and elongation of the saturated polyurethaneelastomers. Suitable UV absorbers and light stabilizers include TINUVIN®328, TINUVIN® 213, TINUVIN® 765, TINUVIN® 770 and TINUVIN® 622. Thepreferred UV absorber is TINUVIN® 328, and the preferred lightstabilizer is TINUVIN® 765. TINUVIN® products are available fromCiba-Geigy. Dyes, as well as optical brighteners and fluorescentpigments may also be included in the golf ball covers produced withpolymers formed according to the present invention. Such additionalingredients may be added in any amounts that will achieve their desiredpurpose.

Any method known to one of ordinary skill in the art may be used topolyurethanes of the present invention. One commonly employed method,known in the art as a one-shot method, involves concurrent mixing of thepolyisocyanate, polyol, and curing agent. This method results in amixture that is inhomogeneous (more random) and affords the manufacturerless control over the molecular structure of the resultant composition.A preferred method of mixing is known as a prepolymer method. In thismethod, the polyisocyanate and the polyol are mixed separately prior toaddition of the curing agent. This method affords a more homogeneousmixture resulting in a more consistent polymer composition. Othermethods suitable for forming the layers of the present invention includereaction injection molding (“RIM”), liquid injection molding (“LIM”),and pre-reacting the components to faun an injection moldablethermoplastic polyurethane and then injection molding, all of which areknown to one of ordinary skill in the art.

Additional components which can be added to the polyurethane compositioninclude UV stabilizers and other dyes, as well as optical brightenersand fluorescent pigments and dyes. Such additional ingredients may beadded in any amounts that will achieve their desired purpose. It hasbeen found by the present invention that the use of a castable, reactivematerial, which is applied in a fluid form, makes it possible to obtainvery thin outer cover layers on golf balls. Specifically, it has beenfound that castable, reactive liquids, which react to form a urethaneelastomer material, provide desirable very thin outer cover layers.

The castable, reactive liquid employed to form the urethane elastomermaterial can be applied over the core using a variety of applicationtechniques such as spraying, dipping, spin coating, or flow coatingmethods which are well known in the art. An example of a suitablecoating technique is that which is disclosed in U.S. Pat. No. 5,733,428,the disclosure of which is hereby incorporated by reference in itsentirety.

The outer cover is preferably formed around the inner cover by mixingand introducing the material in the mold halves. It is important thatthe viscosity be measured over time, so that the subsequent steps offilling each mold half, introducing the core into one half and closingthe mold can be properly timed for accomplishing centering of the corecover halves fusion and achieving overall uniformity. Suitable viscosityrange of the curing urethane mix for introducing cores into the moldhalves is determined to be approximately between about 2,000 cP andabout 30,000 cP, with the preferred range of about 8,000 cP to about15,000 cP.

To start the cover formation, mixing of the prepolymer and curative isaccomplished in motorized mixer including mixing head by feeding throughlines metered amounts of curative and prepolymer. Top preheated moldhalves are filled and placed in fixture units using centering pinsmoving into holes in each mold. At a later time, a bottom mold half or aseries of bottom mold halves have similar mixture amounts introducedinto the cavity. After the reacting materials have resided in top moldhalves for about 40 to about 80 seconds, a core is lowered at acontrolled speed into the gelling reacting mixture.

A ball cup holds the ball core through reduced pressure (or partialvacuum). Upon location of the coated core in the halves of the moldafter gelling for about 40 to about 80 seconds, the vacuum is releasedallowing core to be released. The mold halves, with core and solidifiedcover half thereon, are removed from the centering fixture unit,inverted and mated with other mold halves which, at an appropriate timeearlier, have had a selected quantity of reacting polyurethaneprepolymer and curing agent introduced therein to commence gelling.

Similarly, U.S. Pat. No. 5,006,297 to Brown et al. and U.S. Pat. No.5,334,673 to Wu both also disclose suitable molding techniques which maybe utilized to apply the castable reactive liquids employed in thepresent invention. Further, U.S. Pat. Nos. 6,180,040 and 6,180,722disclose methods of preparing dual core golf balls. The disclosures ofthese patents are hereby incorporated by reference in their entirety.However, the method of the invention is not limited to the use of thesetechniques.

Depending on the desired properties, balls prepared according to theinvention can exhibit substantially the same or higher resilience, orcoefficient of restitution (“COR”), with a decrease in compression ormodulus, compared to balls of conventional construction. Additionally,balls prepared according to the invention can also exhibit substantiallyhigher resilience, or COR, without an increase in compression, comparedto balls of conventional construction. Another measure of thisresilience is the “loss tangent,” or tan δ, which is obtained whenmeasuring the dynamic stiffness of an object. Loss tangent andterminology relating to such dynamic properties is typically describedaccording to ASTM D4092-90. Thus, a lower loss tangent indicates ahigher resiliency, thereby indicating a higher rebound capacity. Lowloss tangent indicates that most of the energy imparted to a golf ballfrom the club is converted to dynamic energy, i.e., launch velocity andresulting longer distance. The rigidity or compressive stiffness of agolf ball may be measured, for example, by the dynamic stiffness. Ahigher dynamic stiffness indicates a higher compressive stiffness. Toproduce golf balls having a desirable compressive stiffness, the dynamicstiffness of the crosslinked reaction product material should be lessthan about 50,000 N/m at −50° C. Preferably, the dynamic stiffnessshould be between about 10,000 and 40,000 N/m at −50° C., morepreferably, the dynamic stiffness should be between about 20,000 and30,000 N/m at −50° C.

The molding process and composition of golf ball portions typicallyresults in a gradient of material properties. Methods employed in theprior art generally exploit hardness to quantify these gradients.Hardness is a qualitative measure of static modulus and does notrepresent the modulus of the material at the deformation ratesassociated with golf ball use, i.e., impact by a club. As is well knownto one skilled in the art of polymer science, the time-temperaturesuperposition principle may be used to emulate alternative deformationrates. For golf ball portions including polybutadiene, a 1-Hzoscillation at temperatures between 0° C. and −50° C. are believed to bequalitatively equivalent to golf ball impact rates. Therefore,measurement of loss tangent and dynamic stiffness at 0° C. to −50° C.may be used to accurately anticipate golf ball performance, preferablyat temperatures between about −20° C. and −50° C.

In another embodiment of the present invention, a golf ball of thepresent invention is substantially spherical and has a cover with aplurality of dimples formed on the outer surface thereof.

U.S. application Ser. No. 10/230,015, now U.S. Publication No.2003/0114565, and U.S. application Ser. No. 10/108,793, now U.S.Publication No. 2003/0050373, which are incorporated by reference hereinin their entirety, discuss soft, high resilient ionomers, which arepreferably from neutralizing the acid copolymer(s) of at least one E/X/Ycopolymer, where E is ethylene, X is the α,β-ethylenically unsaturatedcarboxylic acid, and Y is a softening co-monomer. X is preferablypresent in 2-30 (preferably 4-20, most preferably 5-15) wt. % of thepolymer, and Y is preferably present in 17-40 (preferably 20-40, andmore preferably 24-35) wt. % of the polymer. Preferably, the melt index(MI) of the base resin is at least 20, or at least 40, more preferably,at least 75 and most preferably at least 150. Particular soft, resilientionomers included in this invention are partially neutralizedethylene/(meth) acrylic acid/butyl(meth)acrylate copolymers having an MIand level of neutralization that results in a melt processible polymerthat has useful physical properties. The copolymers are at leastpartially neutralized. Preferably at least 40, or, more preferably atleast 55, even more preferably about 70, and most preferably about 80 ofthe acid moiety of the acid copolymer is neutralized by one or morealkali metal, transition metal, or alkaline earth metal cations. Cationsuseful in making the ionomers of this invention comprise lithium,sodium, potassium, magnesium, calcium, barium, or zinc, or a combinationof such cations.

The invention also relates to a “modified” soft, resilient thermoplasticionomer that comprises a melt blend of (a) the acid copolymers or themelt processible ionomers made therefrom as described above and (b) oneor more organic acid(s) or salt(s) thereof, wherein greater than 80%,preferably greater than 90% of all the acid of (a) and of (b) isneutralized. Preferably, 100% of all the acid of (a) and (b) isneutralized by a cation source. Preferably, an amount of cation sourcein excess of the amount required to neutralize 100% of the acid in (a)and (b) is used to neutralize the acid in (a) and (b). Blends with fattyacids or fatty acid salts are preferred.

The organic acids or salts thereof are added in an amount sufficient toenhance the resilience of the copolymer. Preferably, the organic acidsor salts thereof are added in an amount sufficient to substantiallyremove remaining ethylene crystallinity of the copolymer.

Preferably, the organic acids or salts are added in an amount of atleast about 5% (weight basis) of the total amount of copolymer andorganic acid(s). More preferably, the organic acids or salts thereof areadded in an amount of at least about 15%, even more preferably at leastabout 20%. Preferably, the organic acid(s) are added in an amount up toabout 50% (weight basis) based on the total amount of copolymer andorganic acid. More preferably, the organic acids or salts thereof areadded in an amount of up to about 40%, more preferably, up to about 35%.The non-volatile, non-migratory organic acids preferably are one or morealiphatic, mono-functional organic acids or salts thereof as describedbelow, particularly one or more aliphatic, mono-functional, saturated orunsaturated organic acids having less than 36 carbon atoms or salts ofthe organic acids, preferably stearic acid or oleic acid. Fatty acids orfatty acid salts are most preferred.

Processes for fatty acid (salt) modifications are known in the art.Particularly, the modified highly-neutralized soft, resilient acidcopolymer ionomers of this invention can be produced by:

(a) melt-blending (1) ethylene, α,β-ethylenically unsaturated C₃₋₈carboxylic acid copolymer(s) or melt-processible ionomer(s) thereof thathave their crystallinity disrupted by addition of a softening monomer orother means with (2) sufficient non-volatile, non-migratory organicacids to substantially enhance the resilience and to disrupt (preferablyremove) the remaining ethylene crystallinity, and then concurrently orsubsequently

(b) adding a sufficient amount of a cation source to increase the levelof neutralization of all the acid moieties (including those in the acidcopolymer and in the organic acid if the non-volatile, non-migratoryorganic acid is an organic acid) to the desired level.

The weight ratio of X to Y in the composition is at least about 1:20.Preferably, the weight ratio of X to Y is at least about 1:15, morepreferably, at least about 1:10. Furthermore, the weight ratio of X to Yis up to about 1:1.67, more preferably up to about 1:2. Most preferably,the weight ratio of X to Y in the composition is up to about 1:2.2.

The acid copolymers used in the present invention to make the ionomersare preferably ‘direct’ acid copolymers (containing high levels ofsoftening monomers). As noted above, the copolymers are at leastpartially neutralized, preferably at least about 40% of X in thecomposition is neutralized. More preferably, at least about 55% of X isneutralized. Even more preferably, at least about 70, and mostpreferably, at least about 80% of X is neutralized. In the event thatthe copolymer is highly neutralized (e.g., to at least 45%, preferably50%, 55%, 70%, or 80%, of acid moiety), the MI of the acid copolymershould be sufficiently high so that the resulting neutralized resin hasa measurable MI in accord with ASTM D-1238, condition E, at 190° C.,using a 2160 gram weight. Preferably this resulting MI will be at least0.1, preferably at least 0.5, and more preferably 1.0 or greater.Preferably, for highly neutralized acid copolymer, the MI of the acidcopolymer base resin is at least 20, or at least 40, at least 75, andmore preferably at least 150.

The acid copolymers preferably comprise alpha olefin, particularlyethylene, C₃₋₈. α,β-ethylenically unsaturated carboxylic acid,particularly acrylic and methacrylic acid, and softening monomers,selected from alkyl acrylate, and alkyl methacrylate, wherein the alkylgroups have from 1-8 carbon atoms, copolymers. By “softening,” it ismeant that the crystallinity is disrupted (the polymer is made lesscrystalline). While the alpha olefin can be a C₂-C₄ alpha olefin,ethylene is most preferred for use in the present invention.Accordingly, it is described and illustrated herein in terms of ethyleneas the alpha olefin.

The acid copolymers, when the alpha olefin is ethylene, can be describedas E/X/Y copolymers where E is ethylene, X is the α,β-ethylenicallyunsaturated carboxylic acid, and Y is a softening comonomer; X ispreferably present in 2-30 (preferably 4-20, most preferably 5-15) wt. %of the polymer, and Y is preferably present in 17-40 (preferably 20-40,most preferably 24-35) wt. % of the polymer.

The ethylene-acid copolymers with high levels of acid (X) are difficultto prepare in continuous polymerizers because of monomer-polymer phaseseparation. This difficulty can be avoided however by use of “co-solventtechnology” as described in U.S. Pat. No. 5,028,674, or by employingsomewhat higher pressures than those which copolymers with lower acidcan be prepared.

Specific acid-copolymers include ethylene/(meth) acrylicacid/n-butyl(meth)acrylate, ethylene/(meth) acrylicacid/iso-butyl(meth)acrylate, ethylene/(meth) acrylic acid/methyl(meth)acrylate, and ethylene/(meth) acrylic acid/ethyl(meth)acrylateterpolymers.

The organic acids employed are aliphatic, mono-functional (saturated,unsaturated, or multi-unsaturated) organic acids, particularly thosehaving fewer than 36 carbon atoms. Also salts of these organic acids maybe employed. Fatty acids or fatty acid salts are preferred. The saltsmay be any of a wide variety, particularly including the barium,lithium, sodium, zinc, bismuth, potassium, strontium, magnesium orcalcium salts of the organic acids. Particular organic acids useful inthe present invention include caproic acid, caprylic acid, capric acid,lauric acid, stearic acid, behenic acid, erucic acid, oleic acid, andlinoleic acid.

The optional filler component is chosen to impart additional density toblends of the previously described components, the selection beingdependent upon the different parts (e.g., cover, mantle, core, center,intermediate layers in a multilayered core or ball) and the type of golfball desired (e.g., one-piece, two-piece, three-piece or multiple-pieceball), as will be more fully detailed below.

Generally, the filler will be inorganic having a density greater thanabout 4 g/cm³, preferably greater than 5 g/cm³, and will be present inamounts between 0 to about 60 wt. % based on the total weight of thecomposition. Examples of useful fillers include zinc oxide, bariumsulfate, lead silicate and tungsten carbide, as well as the otherwell-known fillers used in golf balls. It is preferred that the fillermaterials be non-reactive or almost non-reactive and not stiffen orraise the compression nor reduce the coefficient of restitutionsignificantly.

Additional optional additives useful in the practice of the subjectinvention include acid copolymer wax (e.g., Allied wax AC 143 believedto be an ethylene/16-18% acrylic acid copolymer with a number averagemolecular weight of 2,040), which assist in preventing reaction betweenthe filler materials (e.g., ZnO) and the acid moiety in the ethylenecopolymer. Other optional additives include TiO₂, which is used as awhitening agent; optical brighteners; surfactants; processing aids; etc.

Ionomers may be blended with conventional ionomeric copolymers (di-,ter-, etc.), using well-known techniques, to manipulate productproperties as desired. The blends would still exhibit lower hardness andhigher resilience when compared with blends based on conventionalionomers.

Also, ionomers can be blended with non-ionic thermoplastic resins tomanipulate product properties. The non-ionic thermoplastic resins would,by way of non-limiting illustrative examples, include thermoplasticelastomers, such as polyurethane, poly-ether-ester, poly-amide-ether,polyether-urea, PEBAX® (a family of block copolymers based onpolyether-block-amide, commercially supplied by Atochem),styrene-butadiene-styrene (SBS) block copolymers,styrene(ethylene-butylene)-styrene block copolymers, etc., polyamide(oligomeric and polymeric), polyesters, polyolefins including PE, PP,E/P copolymers, etc., ethylene copolymers with various comonomers, suchas vinyl acetate, (meth)acrylates, (meth)acrylic acid,epoxy-functionalized monomer, CO, etc., functionalized polymers withmaleic anhydride grafting, epoxidization etc., elastomers, such as EPDM,metallocene catalyzed PE and copolymer, ground up powders of thethermoset elastomers, etc. Such thermoplastic blends comprise about 1%to about 99% by weight of a first thermoplastic and about 99% to about1% by weight of a second thermoplastic.

Additionally, the compositions of U.S. Pat. Nos. 6,953,820 and6,653,382, both of which are incorporated herein in their entirety,discuss compositions having high COR when formed into solid spheres.

The thermoplastic composition of this invention comprises a polymerwhich, when formed into a sphere that is 1.50 to 1.54 inches indiameter, has a coefficient of restitution when measured by firing thesphere at an initial velocity of 125 ft/s against a steel platepositioned 3 ft from the point where initial velocity and reboundvelocity are determined and by dividing the rebound velocity from theplate by the initial velocity and an Atti compression of no more than100.

Initial velocity of a golf ball after impact with a golf club isgoverned by the United States Golf Association (“USGA”). The USGArequires that a regulation golf ball can have an initial velocity of nomore than 250 ft/s±2% (effectively 255 ft/s). The USGA initial velocitylimit is related to the ultimate distance that a golf ball may travel(280 yards±6%), and is also related to the COR. The COR is the ratio ofthe a) relative velocity between two objects after direct impact to theb) relative velocity before impact. As a result, the COR can vary from 0to 1.0, with 1.0 being equivalent to a perfectly or completely elasticcollision and 0 being equivalent to a perfectly plastic or completelyinelastic collision.

One conventional technique for measuring COR uses a golf ball or sphere,an air cannon, and a stationary steel plate. The steel plate provides animpact surface weighing about 100 lb (45 kg). A pair of ballistic lightscreens, which measure ball velocity, are spaced apart and locatedbetween the air cannon and the steel plate. The golf ball is fired fromthe air cannon toward the steel plate over a range of test velocitiesfrom 50 ft/s to 180 ft/s. As the ball travels toward the steel plate, itactivates each light screen so that the time at each light screen ismeasured. This provides an incoming time period proportional to the ballincoming velocity. The ball impacts the steel plate and rebounds thoughthe light screens, which again measure the time period required totransit between the light screens. This provides an outgoing transittime period proportional to the ball outgoing velocity. The COR can becalculated by the ratio of the outgoing transit time period to theincoming transit time period, COR=T_(out)/T_(in).

Another COR measuring method uses a titanium disk. The titanium disk,intending to simulate a golf club, is circular and has a diameter ofabout 4 inches and has a mass of about 200 g. The impact face of thetitanium disk may also be flexible and has its own COR, as discussedfurther below. The disk is mounted on an X—Y—Z table so that itsposition can be adjusted relative to the launching device prior totesting. A pair of ballistic light screens are spaced apart and locatedbetween the launching device and the titanium disk. The ball is firedfrom the launching device toward the titanium disk at a predeterminedtest velocity. As the ball travels toward the titanium disk, itactivates each light screen so that the time period to transit betweenthe light screens is measured. This provides an incoming transit timeperiod proportional to the ball incoming velocity. The ball impacts thetitanium disk, and rebounds through the light screens which measure thetime period to transit between the light screens. This provides anoutgoing transit time period proportional to the ball's outgoingvelocity. Coefficient of restitution can be calculated from the ratio ofthe outgoing time period to the incoming time period along with the massof the disk and ball: COR=[(T_(out)/T_(in))(M_(e)+M_(b))+M_(b)]/M_(e).

The thermoplastic composition of this invention preferably comprises (a)aliphatic, mono-functional organic acid(s) having fewer than 36 carbonatoms; and (b) ethylene, C₃ to C₈ α,β-ethylenically unsaturatedcarboxylic acid copolymer(s) and ionomer(s) thereof, wherein greaterthan 90%, preferably near 100%, and more preferably 100% of all the acidof (a) and (b) are neutralized.

The thermoplastic composition preferably comprises melt-processible,highly-neutralized (greater than 90%, preferably near 100%, and morepreferably 100%) polymer of (1) ethylene, C₃ to C₈ α,β-ethylenicallyunsaturated carboxylic acid copolymers that have their crystallinitydisrupted by addition of a softening monomer or other means such as highacid levels, and (2) non-volatile, non-migratory agents such as organicacids (or salts) selected for their ability to substantially or totallysuppress any remaining ethylene crystallinity. Agents other than organicacids (or salts) may be used.

It has been found that, by modifying an acid copolymer or ionomer with asufficient amount of specific organic acids (or salts thereof); it ispossible to highly neutralize the acid copolymer without losingprocessability or properties such as elongation and toughness. Theorganic acids employed in the present invention are aliphatic,mono-functional, saturated or unsaturated organic acids, particularlythose having fewer than 36 carbon atoms, and particularly those that arenon-volatile and non-migratory and exhibit ionic array plasticizing andethylene crystallinity suppression properties.

With the addition of sufficient organic acid, greater than 90%, nearly100%, and preferably 100% of the acid moieties in the acid copolymerfrom which the ionomer is made can be neutralized without losing theprocessability and properties of elongation and toughness.

The melt-processible, highly-neutralized acid copolymer ionomer can beproduced by the following:

(a) melt-blending (1) ethylene α,β-ethylenically unsaturated C₃₋₈carboxylic acid copolymer(s) or melt-processible ionomer(s) thereof(ionomers that are not neutralized to the level that they have becomeintractable, that is not melt-processible) with (1) one or morealiphatic, mono-functional, saturated or unsaturated organic acidshaving fewer than 36 carbon atoms or salts of the organic acids, andthen concurrently or subsequently

(b) adding a sufficient amount of a cation source to increase the levelof neutralization all the acid moieties (including those in the acidcopolymer and in the organic acid) to greater than 90%, preferably near100%, more preferably to 100%.

Preferably, highly-neutralized thermoplastics of the invention can bemade by:

(a) melt-blending (1) ethylene, α,β-ethylenically unsaturated C₃₋₈carboxylic acid copolymer(s) or melt-processible ionomer(s) thereof thathave their crystallinity disrupted by addition of a softening monomer orother means with (2) sufficient non-volatile, non-migratory agents tosubstantially remove the remaining ethylene crystallinity, and thenconcurrently or subsequently

(b) adding a sufficient amount of a cation source to increase the levelof neutralization all the acid moieties (including those in the acidcopolymer and in the organic acid if the non-volatile, non-migratoryagent is an organic acid) to greater than 90%, preferably near 100%,more preferably to 100%.

The acid copolymers used in the present invention to make the ionomersare preferably ‘direct’ acid copolymers. They are preferably alphaolefin, particularly ethylene, C₃₋₈ α,β-ethylenically unsaturatedcarboxylic acid, particularly acrylic and methacrylic acid, copolymers.They may optionally contain a third softening monomer. By “softening,”it is meant that the crystallinity is disrupted (the polymer is madeless crystalline). Suitable “softening” comonomers are monomers selectedfrom alkyl acrylate, and alkyl methacrylate, wherein the alkyl groupshave from 1-8 carbon atoms.

The acid copolymers, when the alpha olefin is ethylene, can be describedas E/X/Y copolymers where E is ethylene, X is the α,β-ethylenicallyunsaturated carboxylic acid, and Y is a softening comonomer. X ispreferably present in 3-30 (preferably 4-25, most preferably 5-20) wt. %of the polymer, and Y is preferably present in 0-30 (alternatively 3-25or 10-23) wt. % of the polymer.

In one embodiment, golf balls made with the cores of the invention enjoyhigh COR at relatively low club speeds. The COR of these balls is higherthan the COR of similar balls with higher compression cores atrelatively low club speeds. At higher club speeds, however, the COR ofgolf balls with low compression cores can be lower than the COR of ballswith higher compression cores. As illustrated herein, a first golf ballwith a 1.505-inch diameter core and a core compression of 48(hereinafter “Sample-48”) and a second golf ball with a 1.515-inchdiameter core and a core compression of 80 (hereinafter “Sample-80”)were subject to the following distance and COR tests. Sample-48 andSample-80 have essentially the same size core and similar dual-layercover. The single most significant difference between these two balls isthe compression of the respective cores.

As used in the ball speed test, the “average driver set-up” refers to aset of launch conditions, i.e., at a club head speed to which amechanical golf club has been adjusted so as to generate a ball speed ofabout 140 ft/s. Similarly, the “standard driver set-up” refers to asimilar ball speed at launch conditions of about 160 ft/s; the “Pro 167set-up” refers to a ball speed at launch conditions of about 167 ft/s;and the “Big Pro 175 set-up” refers to a ball speed at launch conditionsof about 175 ft/s. Also, as used in the COR test, the mass plate is a45-kg plate (100 lb) against which the balls strike at the indicatedspeed. The 200-g solid plate is a smaller mass that the balls strike andresembles the mass of a club head. The 199.8-g calibration plateresembles a driver with a flexible face that has a COR of 0.830.

The ball speed test results show that while Sample-48 holds a ball speedadvantage at club speeds of 140 ft/s to 160 ft/s launch conditions,Sample-80 decidedly has better ball speed at 167 ft/s and 175 ft/slaunch conditions.

Similarly, the COR test results show that at the higher collision speed(160 ft/s), the COR generally goes down for both balls, but the 199.8-gcalibration test shows that the COR of the higher compression Sample-80is significantly better than the lower compression Sample-48 at thecollision speed (160 ft/s). Additionally, while the COR generally goesdown for both balls, the rate of decrease is much less for Sample-80than for Sample-48. Unless specifically noted, COR values used hereafterare measured by either the mass plate method or the 200-gram solid platemethod, i.e., where the impact plate is not flexible. Unless otherwisenoted, COR values used hereafter are measured by either the mass platemethod or the 200-g solid plate method.

Without being limited to any particular theory, the inventors of thepresent invention believe that at high impact, the ball with lower corecompression deforms more than the ball with higher core compression.Such deformation negatively affects the initial velocity and COR of theball.

In accordance to the present invention, a golf ball is provided with alow compression and high COR layer, which is supported or otherwisereinforced by a low deformation layer.

On the other hand, the low deformation layer in accordance to thepresent invention may comprise a durable, low deformation material suchas metal, rigid plastics, or polymers re-enforced with high strengthorganic or inorganic fillers or fibers, or blends or composites thereof,as discussed below. Suitable plastics or polymers include, but notlimited to, high cis- or trans-polybutadiene, one or more of partiallyor fully neutralized ionomers including those neutralized by a metal ionsource wherein the metal ion is the salt of an organic acid, polyolefinsincluding polyethylene, polypropylene, polybutylene and copolymersthereof including polyethylene acrylic acid or methacrylic acidcopolymers, or a terpolymer of ethylene, a softening acrylate classester such as methyl acrylate, n-butyl-acrylate or iso-butyl-acrylate,and a carboxylic acid such as acrylic acid or methacrylic acid (e.g.,terpolymers including polyethylene-methacrylic acid-n or iso-butylacrylate and polyethylene-acrylic acid-methyl acrylate, polyethyleneethyl or methyl acrylate, polyethylene vinyl acetate, polyethyleneglycidyl alkyl acrylates). Suitable polymers also include metallocenecatalyzed polyolefins, polyesters, polyamides, non-ionomericthermoplastic elastomers, copolyether-esters, copolyether-amides, EPR,EPDM, thermoplastic or thermosetting polyurethanes, polyureas,polyurethane ionomers, epoxies, polycarbonates, polybutadiene,polyisoprene, and blends thereof. In the case of metallocenes, thepolymer may be cross-linked with a free radical source, such asperoxide, or by high radiation.

Spheres were prepared using fully neutralized ionomers A and B.

TABLE I Cation (% Sample Resin Type (%) Acid Type (%) neut*) M.I. (g/10min) 1A A (60) Oleic (40) Mg (100) 1.0 2B A (60) Oleic (40) Mg (105)*0.9 3C B (60) Oleic (40) Mg (100) 0.9 4D B (60) Oleic (40) Mg (105)* 0.95E B (60) Stearic (40) Mg (100) 0.85 A - 76.9% ethylene 14.8% normalbutyl acrylate, 8.3% acrylic acid B - 75% ethylene, 14.9% normal butylacrylate, 10.1% acrylic acid *indicates that cation was sufficient toneutralize 105% of all the acid in the resin and the organic acid.

These compositions were molded into 1.53-inch spheres for which data ispresented in the following table.

TABLE II Sample Atti Compression COR @ 125 ft/s 1A 75 0.826 2B 75 0.8263C 78 0.837 4D 76 0.837 5E 97 0.807

Further testing of commercially available highly neutralized polymersHNP1 and HNP2 had the following properties.

TABLE III Material Properties HNP1 HNP2 Specific Gravity (g/cm³) 0.9660.974 Melt Flow, 190° C., 10-kg load 0.65 1.0 Shore D Flex Bar (40 hr)47.0 46.0 Shore D Flex Bar (2 week) 51.0 48.0 Flex Modulus, psi (40 hr)25,800 16,100 Flex Modulus, psi (2 week) 39,900 21,000 DSC Melting Point(° C.) 61.0 61/101 Moisture (ppm) 1500 4500 Weight % Mg 2.65 2.96

TABLE IV Solid Sphere Data HNP1a/HNP2a Material HNP1 HNP2 HNP2a HNP1a(50:50 blend) Spec. Grav. 0.954 0.959 1.153 1.146 1.148 (g/cm³) FillerNone None Tungsten Tungsten Tungsten Compression 107 83 86 62 72 COR0.827 0.853 0.844 0.806 0.822 Shore D 51 47 49 42 45 Shore C 79 72 75

These materials are exemplary examples of the preferred center and/orcore layer compositions of the present invention. They may also be usedas a cover layer herein.

The golf ball components of the present invention, in particular thecore (center and/or outer core layers) may be formed from a co-polymerof ethylene and an α,β-unsaturated carboxylic acid. In anotherembodiment, they may be formed from a terpolymer of ethylene, anα,β-unsaturated carboxylic acid, and an n-alkyl acrylate. Preferably,the α,β-unsaturated carboxylic acid is acrylic acid or methacrylic acid.In a preferred embodiment, the n-alkyl acrylate is n-butyl acrylate.Further, in a preferred form, the co- or ter-polymer comprises a levelof fatty acid salt greater than 5 phr of the base resin. The preferredfatty acid salt is magnesium oleate or magnesium stearate.

It is highly preferred that the carboxylic acid in the intermediatelayer is 100% neutralized with metal ions. The metal ions used toneutralize the carboxylic acid may be any metal ion known in the art.Preferably, the metal ions comprise magnesium ions. If the material usedin the intermediate layer is not 100% neutralized, the resultantresilience properties such as COR and initial velocity may not besufficient to produce the improved initial velocity and distanceproperties of the present invention.

The golf ball components can comprise various levels of the threecomponents of the co- or terpolymer as follows: from about 60 to about90% ethylene, from about 8 to about 20% by weight of the α,β-unsaturatedcarboxylic acid, and from 0% to about 25% of the n-alkyl acrylate. Theco- or terpolymer may also contain an amount of a fatty acid salt. Thefatty acid salt preferably comprises magnesium oleate. These materialsare commercially available from DuPont, under the tradename DuPont HPF®.

In one embodiment, the core and/or core layers (or other intermediatelayers) comprises a copolymer of about 81% by weight ethylene and about19% by weight acrylic acid, wherein 100% of the carboxylic acid groupsare neutralized with magnesium ions. The copolymer also contains atleast 5 phr of magnesium oleate. Material suitable for use as this layeris available from DuPont under the tradename DuPont HPF SEP 1313-4®.

In a second preferred embodiment, the core and/or core layers (or otherintermediate layers) comprise a copolymer of about 85% by weightethylene and about 15% by weight acrylic acid, wherein 100% of the acidgroups are neutralized with magnesium ions. The copolymer also containsat least 5 phr of magnesium oleate. Material suitable for use as thislayer is available from DuPont under the tradename DuPont HPF SEP1313-3®.

In a third preferred embodiment, the core and/or core layers (or otherintermediate layers) comprise a copolymer of about 88% by weightethylene and about 12% by weight acrylic acid, wherein 100% of the acidgroups are neutralized with magnesium ions. The copolymer also containsat least 5 phr of magnesium oleate. Material suitable for use as thislayer is available from DuPont under the tradename DuPont HPF AD1027®.

In a further preferred embodiment, the core and/or core layers (or otherintermediate layers) are adjusted to a target specific gravity to enablethe ball to be balanced. For a 1.68-inch diameter golf ball having aball weight of about 1.61 oz, the target specific gravity is about1.125. It will be appreciated by one of ordinary skill in the art thatthe target specific gravity will vary based upon the size and weight ofthe golf ball. The specific gravity is adjusted to the desired targetthrough the use of inorganic fillers. Preferred fillers used forcompounding the inner layer to the desired specific gravity include, butare not limited to, tungsten, zinc oxide, barium sulfate and titaniumdioxide. Other suitable fillers, in particular nano or hybrid materials,include those described in U.S. Pat. No. 6,793,592 and U.S. applicationSer. No. 10/037,987, which are incorporated herein, in their entirety,by reference thereto.

Some preferred golf ball layers formed from the above compositions weremolded onto a golf ball center using DuPont HPF RX-85®, Dupont HPF SEP1313-3®, or DuPont HPF SEP 1313-4®. 1) DuPont HPF RX-85®, a copolymer ofabout 88% ethylene and about 12% acrylic acid, wherein 100% of the acidgroups are neutralized with magnesium ions. Further, the copolymercontains a fixed amount of magnesium oleate. This material wascompounded to a specific gravity of about 1.125 using tungsten. TheShore D hardness of this material (as measured on the curved surface ofthe inner cover layer) was about 58 to about 60. 2) DuPont HPF SEP1313-3®, a copolymer of about 85% ethylene and about 15% acrylic acid,wherein 100% of the acid groups are neutralized with magnesium ions.Further, the copolymer contains a fixed amount of magnesium oleate. Thismaterial was compounded to a specific gravity of about 1.125 usingtungsten. The Shore D hardness of this material (as measured on thecurved surface of the inner cover layer) was about 58-60. 3) DuPont HPFSEP 1313-4®, a copolymer of about 81% ethylene and about 19% acrylicacid, wherein 100% of the acid groups are neutralized with magnesiumions. Further, the copolymer contains a fixed amount of magnesiumoleate. This material was compounded to a specific gravity of about1.125 using tungsten. The Shore D hardness of this material (as measuredon the curved surface of the inner cover layer) was about 58-60.

The centers/cores/layers can also comprise various levels of the threecomponents of the terpolymer as follows: from about 60% to 80% ethylene;from about 8% to 20% by weight of the α,β-unsaturated carboxylic acid;and from about 0% to 25% of the n-alkyl acrylate, preferably 5% to 25%.The terpolymer will also contain an amount of a fatty acid salt,preferably magnesium oleate. These materials are commercially availableunder the trade name DuPont® HPF™. In a preferred embodiment, aterpolymer suitable for the invention will comprise from about 75% to80% by weight ethylene, from about 8% to 12% by weight of acrylic acid,and from about 8% to 17% by weight of n-butyl acrylate, wherein all ofthe carboxylic acid is neutralized with magnesium ions, and comprises atleast 5 phr of magnesium oleate.

In another preferred embodiment, the cover layer will comprise aterpolymer of about 70% to 75% by weight ethylene, about 10.5% by weightacrylic acid, and about 15.5% to 16.5% by weight n-butyl acrylate. Theacrylic acid groups are 100% neutralized with magnesium ions. Theterpolymer will also contain an amount of magnesium oleate. Materialssuitable for use as this layer are sold under the trade name DuPont®HPF™ AD 1027.

In yet another preferred embodiment, the centers/cores/layers comprise acopolymer comprising about 88% by weight of ethylene and about 12% byweight acrylic acid, with 100% of the acrylic acid neutralized bymagnesium ions. The centers/cores/layers may also contain magnesiumoleate. Material suitable for this embodiment was produced by DuPont asexperimental product number SEP 1264-3. Preferably thecenters/cores/layers are adjusted to a target specific gravity of 1.125using inert fillers to adjust the density with minimal effect on theperformance properties of the cover layer. Preferred fillers used forcompounding the centers/cores/layers to the desired specific gravityinclude but are not limited to tungsten, zinc oxide, barium sulfate, andtitanium dioxide.

A first set of intermediate layers were molded onto cores using DuPont®HPF™ AD1027, which is a terpolymer of about 73% to 74% ethylene, about10.5% acrylic acid, and about 15.5% to 16.5% n-butyl acrylate, wherein100% of the acid groups are neutralized with magnesium ions. Further,the terpolymer contains a fixed amount of greater than 5 phr magnesiumoleate. This material is compounded to a specific gravity of about 1.125using barium sulfate and titanium dioxide. The Shore D hardness of thismaterial (as measured on the curved surface of the inner cover layer) isabout 58-60.

A second set of layers were molded onto each of the experimental coresusing DuPont experimental HPF™ SEP 1264-3, which is a copolymer of about88% ethylene and about 12% acrylic acid, wherein 100% of the acid groupsare neutralized with magnesium ions. Further, the copolymer contains afixed amount of at least 5 phr magnesium oleate. This material iscompounded to a specific gravity of about 1.125 using zinc oxide. TheShore D hardness of this material (as measured on the curved surface ofthe inner cover layer) is about 61-64.

A first set of covers were molded onto each of the core/layer componentsusing DuPont HPF™ 1000, which is a terpolymer of about 75% to 76%ethylene, about 8.5% acrylic acid, and about 15.5% to 16.5% n-butylacrylate, wherein 100% of the acid groups are neutralized with magnesiumions. Further, the terpolymer contains a fixed amount of at least 5 phrof magnesium stearate. This material is compounded to a target specificgravity of about 1.125 using barium sulfate and titanium dioxide. TheShore D hardness of this material (as measured on the curved surface ofthe molded golf ball) is about 60-62.

In one embodiment, the formation of a golf ball starts with forming theinner core. The inner core, outer core, and the cover are formed bycompression molding, by injection molding, or by casting. These methodsof forming cores and covers of this type are well known in the art. Thematerials used for the inner and outer core, as well as the cover, areselected so that the desired playing characteristics of the ball areachieved. The inner and outer core materials have substantiallydifferent material properties so that there is a predeterminedrelationship between the inner and outer core materials, to achieve thedesired playing characteristics of the ball.

In one embodiment, the inner core is formed of a first material having afirst Shore D hardness, a first elastic modulus, a first specificgravity, and a first Bashore resilience. The outer core is formed of asecond material having a second Shore D hardness, a second elasticmodulus, a second specific gravity, and a second Bashore resilience.Preferably, the material property of the first material equals at leastone selected from the group consisting of the first Shore D hardnessdiffering from the second Shore D hardness by at least 10 points, thefirst elastic modulus differing from the second elastic modulus by atleast 10%, the first specific gravity differing from the second specificgravity by at least 0.1, or a first Bashore resilience differing fromthe second Bashore resilience by at least 10%. It is more preferred thatthe first material have all of these material property relationships.

Moreover, it is preferred that the first material has the first Shore Dhardness between about 30 and about 80, the first elastic modulusbetween about 5,000 psi and about 100,000 psi, the first specificgravity between about 0.8 and about 1.6, and the first Bashoreresilience greater than 30%.

In another embodiment, the first Shore D hardness is less than thesecond Shore D hardness, the first elastic modulus is less than thesecond elastic modulus, the first specific gravity is less than thesecond specific gravity, and the first Bashore resilience is less thanthe second Bashore resilience. In another embodiment, the first materialproperties are greater than the second material properties. Therelationship between the first and second material properties depends onthe desired playability characteristics.

Suitable inner and outer core materials include HNP's neutralized withorganic fatty acids and salts thereof, metal cations, or a combinationof both, thermosets, such as rubber, polybutadiene, polyisoprene;thermoplastics, such as ionomer resins, polyamides or polyesters; orthermoplastic elastomers. Suitable thermoplastic elastomers includePEBAX®, HYTREL®, thermoplastic urethane, and KRATON®, which arecommercially available from Elf-Atochem, DuPont, BF Goodrich, and Shell,respectively. The inner and outer core materials can also be formed froma castable material. Suitable castable materials include, but are notlimited to, urethane, urea, epoxy, diols, or curatives.

The cover is selected from conventional materials used as golf ballcovers based on the desired performance characteristics. The cover maybe comprised of one or more layers. Cover materials such as ionomerresins, blends of ionomer resins, thermoplastic or thermoset urethanes,and balata, can be used as known in the art and discussed above. Inother embodiments, additional layers may be added to those mentionedabove or the existing layers may be formed by multiple materials.

When the core is formed with a fluid-filled center, the center is formedfirst then the inner core is molded around the center. Conventionalmolding techniques can be used for this operation. Then the outer coreand cover are formed thereon, as discussed above. The fluid within theinner core can be a wide variety of materials including air, watersolutions, liquids, gels, foams, hot-melts, other fluid materials andcombinations thereof. The fluid is varied to modify the performanceparameters of the ball, such as the moment of inertia or the spin decayrate. Examples of suitable liquids include either solutions such as saltin water, corn syrup, salt in water and corn syrup, glycol and water oroils. The liquid can further include pastes, colloidal suspensions, suchas clay, barytes, carbon black in water or other liquid, or salt inwater/glycol mixtures. Examples of suitable gels include water gelatingels, hydrogels, water/methyl cellulose gels and gels comprised ofcopolymer rubber based materials such a styrene-butadiene-styrene rubberand paraffinic and/or naphthenic oil. Examples of suitable melts includewaxes and hot melts. Hot-melts are materials which at or about normalroom temperatures are solid but at elevated temperatures become liquid.A high melting temperature is desirable since the liquid core is heatedto high temperatures during the molding of the inner core, outer core,and the cover. The liquid can be a reactive liquid system, whichcombines to form a solid. Examples of suitable reactive liquids aresilicate gels, agar gels, peroxide cured polyester resins, two partepoxy resin systems and peroxide cured liquid polybutadiene rubbercompositions.

The “effective compression constant,” which is designated EC, is theratio of deflection of a 1.50 inch diameter sphere made of any singlematerial used in the core under a 100 kg load that as represented by theformula EC=F/d, where, F is a 100 kg load; and d is the deflection inmillimeters. If the sphere tested is only inner core material, theeffective compression constant for the inner core material alone isdesignated EC_(IC). If the sphere tested is only outer core material,the effective compression constant for the outer core material alone isdesignated EC_(OC). The sum of the constants for the inner core EC_(IC)and outer core EC_(OC) is the constant EC_(S). If the sphere tested isinner and outer core material, the core effective compression constantis designated EC_(C). It is has been determined that very favorablecores are formed when their core effective compression constant EC_(C)is less than the sum of the effective compression constants of the innercore and outer core EC_(S). It is recommended that the core effectivecompression constant EC_(C) is less than about 90% of the sum of theeffective compression constants of the inner core and outer core EC_(S).More preferably, the core effective compression constant EC_(C) is lessthan or equal to about 50% of the sum of the effective compressionconstants of the inner core and outer core EC_(S). The ratios of theinner core material to outer core material and the geometry of the innercore to the outer core are selected to achieve these core effectivecompression constants.

The resultant golf balls typically have a coefficient of restitution ofgreater than about 0.7, preferably greater than about 0.75, and morepreferably greater than about 0.78. The golf balls also typically havean Atti compression of at least about 40, preferably from about 50 to120, and more preferably from about 60 to 100. The golf ball curedpolybutadiene material typically has a hardness of at least about 15Shore A, preferably between about 30 Shore A and 80 Shore D, morepreferably between about 50 Shore A and 60 Shore D.

In addition to the HNP's neutralized with organic fatty acids and saltsthereof, core compositions may comprise at least one rubber materialhaving a resilience index of at least about 40. Preferably theresilience index is at least about 50. Polymers that produce resilientgolf balls and, therefore, are suitable for the present invention,include but are not limited to CB23, CB22, commercially available fromof Bayer Corp. of Orange, Tex., BR60, commercially available fromEnichem of Italy, and 1207G, commercially available from Goodyear Corp.of Akron, Ohio.

Additionally, the unvulcanized rubber, such as polybutadiene, in golfballs prepared according to the invention typically has a Mooneyviscosity of between about 40 and about 80, more preferably, betweenabout 45 and about 65, and most preferably, between about 45 and about55. Mooney viscosity is typically measured according to ASTM-D1646.

When golf balls are prepared according to the invention, they typicallywill have dimple coverage greater than about 60 percent, preferablygreater than about 65 percent, and more preferably greater than about 75percent. The flexural modulus of the cover on the golf balls, asmeasured by ASTM method D6272-98, Procedure B, is typically greater thanabout 500 psi, and is preferably from about 500 psi to 150,000 psi. Asdiscussed herein, the outer cover layer is preferably formed from arelatively soft polyurethane material. In particular, the material ofthe outer cover layer should have a material hardness, as measured byASTM-D2240, less than about 45 Shore D, preferably less than about 40Shore D, more preferably between about 25 and about 40 Shore D, and mostpreferably between about 30 and about 40 Shore D. The casing preferablyhas a material hardness of less than about 70 Shore D, more preferablybetween about 30 and about 70 Shore D, and most preferably, betweenabout 50 and about 65 Shore D.

In a preferred embodiment, the intermediate layer material hardness isbetween about 40 and about 70 Shore D and the outer cover layer materialhardness is less than about 40 Shore D. In a more preferred embodiment,a ratio of the intermediate layer material hardness to the outer coverlayer material hardness is greater than 1.5.

It should be understood, especially to one of ordinary skill in the art,that there is a fundamental difference between “material hardness” and“hardness, as measured directly on a golf ball.” Material hardness isdefined by the procedure set forth in ASTM-D2240 and generally involvesmeasuring the hardness of a flat “slab” or “button” formed of thematerial of which the hardness is to be measured. Hardness, whenmeasured directly on a golf ball (or other spherical surface) is acompletely different measurement and, therefore, results in a differenthardness value. This difference results from a number of factorsincluding, but not limited to, ball construction (i.e., core type,number of core and/or cover layers, etc.), ball (or sphere) diameter,and the material composition of adjacent layers. It should also beunderstood that the two measurement techniques are not linearly relatedand, therefore, one hardness value cannot easily be correlated to theother.

In one embodiment, the core of the present invention has an Atticompression of between about 50 and about 90, more preferably, betweenabout 60 and about 85, and most preferably, between about 65 and about85. The overall outer diameter (“OD”) of the core is less than about1.590 inches, preferably, no greater than 1.580 inches, more preferablybetween about 1.540 inches and about 1.580 inches, and most preferablybetween about 1.525 inches to about 1.570 inches. The OD of the casingof the golf balls of the present invention is preferably between 1.580inches and about 1.640 inches, more preferably between about 1.590inches to about 1.630 inches, and most preferably between about 1.600inches to about 1.630 inches.

Additionally, the core may be a two- or three-piece core, wherein theoutermost core layer is formed from an HNP composition. In a two-piececore embodiment, the center or innermost core layer has a diameter ofabout 1.00 inches to about 1.60 inches, preferably about 1.20 inches toabout 1.58 inches, more preferably about 1.30 inches to about 1.56inches, and most preferably about 1.40 inches to about 1.55 inches. Theoutermost core layer (comprising the HNP composition) typically has athickness of about 0.010 inches to about 0.250 inches, preferably about0.020 inches to about 0.150 inches, more preferably about 0.040 inchesto about 0.125 inches, and most preferably about 0.050 inches to about0.095 inches.

In a three-piece core embodiment, the center or innermost core layer hasa diameter of about 0.25 inches to about 1.50 inches, preferably about0.50 inches to about 1.40 inches, more preferably about 0.75 inches toabout 1.30 inches, and most preferably about 1.0 inches to about 1.20inches. The intermediate core layer (between the innermost core layer(or center) and the outer core layer) typically has a thickness of about0.050 inches to about 0.550 inches, preferably about 0.100 inches toabout 0.300 inches, more preferably about 0.125 inches to about 0.290inches, and most preferably about 0.200 inches to about 0.275 inches.The outermost core layer (comprising HNP) typically has a thickness ofabout 0.010 inches to about 0.250 inches, preferably about 0.020 inchesto about 0.150 inches, more preferably about 0.040 inches to about 0.125inches, and most preferably about 0.050 inches to about 0.095 inches.

In a preferred embodiment, the innermost core (center) has an outersurface hardness that is at least 5 Shore C less than the hardness ofboth the inner and outer surfaces of the outer core layer, preferably atleast 7 Shore C less, most preferably at least 9 Shore C less.

The inner core surface hardness typically ranges from about 50 Shore Cto about 96 Shore C; preferably about 57 Shore C to about 89 Shore C;more preferably about 63 Shore C to about 82 Shore C; most preferablyabout 63 Shore C, 67 Shore C, 71 Shore C, 75 Shore C, or 79 Shore C. Theouter core surface hardness typically ranges from about 57 Shore C toabout 100 Shore C; preferably about 63 Shore C to about 96 Shore C; morepreferably about 70 Shore C to about 89 Shore C; and most preferablyabout 70 Shore C, 74 Shore C, 81 Shore C, 82 Shore C, or 86 Shore C.

In a preferred embodiment, the innermost core (center) has an outersurface hardness that is at least 3 Shore D less than the hardness ofboth the inner and outer surfaces of the outer core layer, preferably atleast 5 Shore D less, more preferably at least 7 Shore D less.

The inner core surface hardness typically ranges from about 30 Shore Dto about 65 Shore D; preferably about 35 Shore D to about 60 Shore D;more preferably about 40 Shore D to about 55 Shore D; most preferablyabout 40 Shore D, 43 Shore D, 46 Shore D, 49 Shore D, or 52 Shore D. Theouter core surface hardness typically ranges from about 35 Shore D toabout 70 Shore D; preferably about 40 Shore D to about 65 Shore D; morepreferably about 45 Shore D to about 60 Shore D; and most preferablyabout 45 Shore D, 48 Shore D, 51 Shore D, 54 Shore D, or 57 Shore D.

The present multilayer golf ball can have an overall diameter of anysize. Although the USGA specifications limit the minimum size of acompetition golf ball to 1.680 inches. There is no specification as tothe maximum diameter. Golf balls of any size, however, can be used forrecreational play. The preferred diameter of the present golf balls isfrom about 1.680 inches to about 1.800 inches. The more preferreddiameter is from about 1.680 inches to about 1.760 inches. The mostpreferred diameter is about 1.680 inches to about 1.740 inches.

The golf balls of the present invention should have a moment of inertia(“MOI”) of less than about 85 and, preferably, less than about 83. TheMOI is typically measured on model number MOI-005-104 MOI Instrumentmanufactured by Inertia Dynamics of Collinsville, Conn. The instrumentis plugged into a PC for communication via a COMM port and is driven byMOI Instrument Software version #1.2. U.S. Pat. Nos. 6,193,619;6,207,784; 6,221,960; 6,414,082; 6,476,130; and 6,287,638 areincorporated in their entirety herein by express reference thereto. Thehighly-neutralized polymers of the present invention may also be used ingolf equipment, in particular, inserts for golf clubs, such as putters,irons, and woods, and in golf shoes and components thereof.

As used herein, the term “about,” used in connection with one or morenumbers or numerical ranges, should be understood to refer to all suchnumbers, including all numbers in a range. Other than in the operatingexamples, or unless otherwise expressly specified, all of the numericalranges, amounts, values and percentages such as those for amounts ofmaterials, and others in the specification may be read as if prefaced bythe word “about” even though the term “about” may not expressly appearwith the value, amount or range. Accordingly, unless indicated to thecontrary, the numerical parameters set forth in the specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Furthermore, when numerical ranges ofvarying scope are set forth herein, it is contemplated that anycombination of these values inclusive of the recited values may be used.The invention described and claimed herein is not to be limited in scopeby the specific embodiments herein disclosed, since these embodimentsare intended solely as illustrations of several aspects of theinvention. Any equivalent embodiments are intended to be within thescope of this invention. Indeed, various modifications of the inventionin addition to those shown and described herein will become apparent tothose skilled in the art from the foregoing description. Suchmodifications are also intended to fall within the scope of the appendedclaims.

1. A golf ball comprising: an inner core layer comprising a first rubbercomposition and having a first surface hardness; an intermediate corelayer comprising a second rubber composition; a thermoplastic outer corelayer having a second surface hardness, an inner surface hardness, andcomprising a copolymer of ethylene and an α,β-unsaturated carboxylicacid, an organic acid or salt thereof, and sufficient cation source tofully-neutralize the acid groups of the copolymer; an inner cover layer;and an outer cover layer; wherein the first surface hardness is lessthan the second surface hardness by at least 5 Shore C and less than theinner surface hardness by at least 5 Shore C.
 2. The golf ball of claim1, wherein the inner core has a diameter of 0.80 inches to 1.40 inchesand a compression of 30 or less, and the outer core layer has flexuralmodulus of 50,000 psi to 70,000 psi and a thickness of 0.040 inches orgreater, and the outer cover layer comprises castable thermosetpolyurethane or polyurea having a hardness of from 45 Shore D to 60Shore D and a thickness from 0.020 inches to 0.040 inches.
 3. The golfball of claim 1, wherein a core resulting from a combination of theinner core layer, the intermediate core layer, and the thermoplasticouter core layer has a compression of 60 or greater.
 4. The golf ball ofclaim 3, wherein the core has a diameter of 1.500 inches or less.
 5. Thegolf ball of claim 4, wherein the outer core layer has a thickness of0.090 inches or greater.
 6. The golf ball of claim 1, wherein the innercore has a first elastic modulus and the outer core layer has a secondelastic modulus less than the first.
 7. The golf ball of claim 1,wherein the inner core has a first specific gravity and the outer corelayer has a second specific gravity less than the first.
 8. The golfball of claim 1, wherein the inner core has a first Bashore resilienceand the outer core layer has a second Bashore resilience less than thefirst.
 9. The golf ball of claim 1, wherein the first surface hardnessis less than the second surface hardness by at least 7 Shore C and lessthan the inner surface hardness by at least 7 Shore C.